CN105273422B - A kind of photic renovation agent of biomaterial pitch and the pitch cementation of fissures cream with its preparation - Google Patents
A kind of photic renovation agent of biomaterial pitch and the pitch cementation of fissures cream with its preparation Download PDFInfo
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- CN105273422B CN105273422B CN201510799786.2A CN201510799786A CN105273422B CN 105273422 B CN105273422 B CN 105273422B CN 201510799786 A CN201510799786 A CN 201510799786A CN 105273422 B CN105273422 B CN 105273422B
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Abstract
Pitch cementation of fissures cream the present invention relates to a kind of photic renovation agent of biomaterial pitch and with its preparation, the wherein photic renovation agent of pitch are made up of net shrimp and crab shells, sodium hydroxide, isopropanol, the methy oxetane of 3 chloromethyl 3, polyethylene glycol and hexamethylene diisocyanate according to certain proportioning；Pitch cementation of fissures cream is by the photic renovation agent of pitch and compatilizer, stabilizer, matrix pitch is made according to certain proportioning, cryogenic property of the renovation agent to pitch, workability, ageing resistace has some improvement, enhance patching material durability, when there is crack again in repair place, under the irradiation of ultraviolet light or sunshine, renovation agent can strengthen the self-healing capability of pitch, so that crack self-healing, extend the service life on road surface, simultaneously, cementation of fissures cream synthesized by the present invention has excellent height, cryogenic property and recoverable force ability, with high softening point, high cryogenic tensile rate and preferable elastic restoration ratio.
Description
Technical field
The invention belongs to highway pavement patching material, and in particular to using biomaterial be biomaterial made of raw material
The photic renovation agent of pitch and preparation method and application its manufactured cementation of fissures cream.
Background technology
The shell of the arthropods such as shrimp, crab is one of organic resource most abundant on the earth, is that fiber is only second on the earth
The organic compounds containing nitrogen of element.China marine site is vast, and shell-fish resource is very abundant, and utilizable quantity is also considerable.
In the last few years, with fresh water and seawater shrimps, the increase of crab cultured output, substantial amounts of shrimp, crab shell produce every year.These are substantial amounts of
Shrimp, crab shell byproduct, the overwhelming majority are thrown away, and cause the wasting of resources, environmental pollution.In recent years, many countries provide for shell-fish
The research and utilization in source have developed rapidly, but for being also short of very much in terms of road.
Because temperature, dry and wet and vehicular load etc. influence crack unavoidably occurs, bituminous paving is opened in bituminous paving
It is one of Major Diseases that countries in the world bituminous paving can all run into split.If these diseases can not be timely repaired,
The normal use performance and service life of bituminous paving can then be influenceed.Therefore, asphalt pavement crack precautionary measures are studied, for carrying
High road transport capacity and service life, increase investment returns, and accelerate social development, have important practical significance.
For crack treatment, the gap-grouting material of generally use has heated bitumen or emulsified asphalt etc. to carry out crack repairing, and
Actually patching material is under traffic load and the warm and humid comprehensive function of environment, general 1 to 2 years, and the crack after repairing fills in original again
Seam position is ftractureed again, and its crash rate can reach more than 85%, and repair efficiency is held time short, influences the normal usage on road surface
Energy and service life.It is not only time consuming if studying for a second time courses one has flunked again, have an effect on the normal operation of traffic.
The content of the invention
In order to overcome the shortcomings of present in asphalt pavement crack self-repair technology, have the invention provides one kind preferable
High and low temperature performance, ageing resistace and recoverable force ability, there is high softening point, high cryogenic tensile rate and can be in illumination
Under the conditions of realize the pitch cementation of fissures cream of selfreparing.
Meanwhile the drip present invention also offers the preparation method of pitch self repairing agent and obtained by with the pitch renovation agent
Blue or green cementation of fissures cream.
Technical scheme is made of raw material of the renovation agent by following proportioning used by the present invention realizes above-mentioned purpose：
The number-average molecular weight of above-mentioned polyethylene glycol is 380~420.
The raw material of the preferably following proportioning of above-mentioned renovation agent：
The pitch cementation of fissures cream prepared with the above-mentioned photic renovation agent of biomaterial pitch, by the raw material system of following quality proportioning
Into：The photic renovation agent of biomaterial pitch is 1 by quality parts ratio with compatilizer, stabilizer and matrix pitch：25~35：
2~4：90~110.
The compatilizer is second line of distillation tapped oil, subtract three line tapped oil or its mixture, and the stabilizer is Sulfur and rubber
Rubber powder is according to 1~2：1 proportioning mixing.
The pitch cementation of fissures cream is made up of following methods：Matrix pitch is heated to 140 DEG C~160 DEG C, add compatilizer and
The photic renovation agent of biomaterial pitch, mix, be heated to 160 DEG C~180 DEG C, stir 40~60min, shear 160~180min,
Stabilizer is added, it is agitated to produce pitch cementation of fissures cream.
The photic renovation agent of biomaterial pitch of the present invention can be poured into directly in pitch crack to be split as renovation agent repairing
Seam, or it is prepared into according to the method described above pitch cementation of fissures cream, after directly can also pour into asphalt pavement crack, so as to repair
Mend crack；When repair place crack occurs again, under the conditions of 0~40 DEG C, 30~50min or solar irradiation are irradiated under ultraviolet light
2~4h, you can selfreparing crack, so as to prevent crack from further expanding.
The photic renovation agent of biomaterial pitch of the present invention has selected biomaterial shrimp and crab shells to utilize routine as raw material
Pickling decalcification, caustic dip take off albumen, concentrated NaOH solution heating synthesis chitosan, recycle chitosan synthesis oxetanes substitution
Chitosan macromonomer, further synthesize polyurethanes network structure the photic reparation of biomaterial pitch
Agent, its building-up process is simple, and can twice laid, cost of material is low, and environmental pollution is small, itself has certain reparation effect
Fruit, and pitch cementation of fissures cream is made according to certain proportioning in itself and matrix pitch and compatilizer, stabilizer, matrix pitch again,
With excellent high and low temperature performance and recoverable force ability, there is high softening point, high cryogenic tensile rate and appropriate elasticity
Recovery rate.Meanwhile the pitch cementation of fissures cream has the performance of illumination selfreparing, when repair place crack occurs again, the pitch cementation of fissures
In cream oxetanes substitution chitosan polyurethanes network structure chemical bond rupture and be produced from
By base, under ultraviolet light, these free radicals will reconfigure, and can repair crack in the process, so as to prevent crack
Further expand, in addition, the renovation agent of the present invention has certain change to the cryogenic property, workability, ageing resistace of pitch
Kind effect, the durability of patching material can be strengthened, extend the service life on road surface, solve the cracking again after cementation of fissures repairing
Problem, more durable repair efficiency is obtained, while also there is the advantages such as environmentally friendly, easy to use, construction cost is low, saved people
Power material resources, preferably solves the problem of Cracking on road surface.
Brief description of the drawings
Fig. 1 is the initial average crack width of pitch (sample one).
Fig. 2 be pitch ultraviolet light 30min reparation after (sample two) average crack width.
Specific embodiment
In conjunction with experiment and embodiment the solution of the present invention is further described, but the present invention be not limited only to it is following
Implementation situation.
Embodiment 1
The photic renovation agent of biomaterial pitch of the present embodiment is made up of following raw material proportioning：
Its preparation can refer to the following step that is collectively referred to as and realize：
(1) 17g shrimp and crab shells are rinsed well, it is small for 10% salt acid soak 8 with the concentration of excess after drying, crush, sieving
When, filtering, shrimp and crab shells are collected, cleaning, remove hydrochloric acid remaining in shrimp and crab shells；It is again 9% with excessive concentration, boiling temps are
90 DEG C of sodium hydroxide solution soaks 3 hours, cools down, filtering, collects shrimp and crab shells, cleaning, removes hydrogen-oxygen remaining in shrimp and crab shells
Change sodium；Then it is soaked 2 hours in the liquor potassic permanganate that concentration is 1%, filters, be in concentration by filtration product
Soak, filter in 1.5% solution of sodium bisulfite, clean, dry, produce chitin；The excessive quality of chitin is dense
Spend for 50%, the sodium hydroxide solution that temperature is 85 DEG C soaks 10 hours, cools down, and filtering, cleans filtration product, removes remnants'
Sodium hydroxide, drying, produces chitosan.
(2) chitosan obtained by step (1) is added in the sodium hydroxide solution that 150ml concentration is 1mol/L, in temperature
Spend to stir 24h under conditions of 0 DEG C, then the 48h that freezes at 0 DEG C, defrosting solution is miscible with isopropanol by it, is stirred at 80 DEG C
1h is mixed, then the 3- chloromethyl -3- methy oxetanes for being preheating to 80 DEG C are added in the mixture and stir 1h, will be preheated to
80 DEG C of 0.15g 3- chloromethyl -3- methy oxetanes, which are added in the mixture, stirs 1h, is filtered and cleaned with methanol
To neutrality, and 12h is dried at 60 DEG C.The product of gained is dispersed in by dimethyl sulfoxide (DMSO) and pH=6.8 acetum,
Then 20min is irradiated with ultraviolet, is separated after product is cleaned with methanol and draw the chitosan that oxetanes substitutes
Macromonomer.
(3) the chitosan macromonomer that the oxetanes obtained by step (2) substitutes is dispersed in dimethyl
In sulfoxide solution, by this mixed solution at 25 DEG C with 12h is ultrasonically treated, then 48h is continuously stirred at 80 DEG C, by the mixed of gained
Close solution to be in nitrogen atmosphere, by chitosan macromonomer that the oxetanes of dispersed substitute, count and divide equally
Son amount is put in 500mL three-necked flasks altogether for 400 polyethylene glycol and 17.5g hexamethylene diisocyanates, adds the bays of 2g bis-
Sour dibutyl tin stirs 10min, mixing speed 300rpm at 25 DEG C, obtains the de- of oxetanes substitution as catalyst
The photic renovation agent of biomaterial pitch of the polyurethanes network structure of acetyl chitin.
The prepared photic renovation agent of biomaterial pitch can be used for preparing pitch cementation of fissures cream, specific method in aforementioned manners
It is as follows：
1000g matrix pitches are heated to 150 DEG C, add 300g second line of distillation tapped oil as compatilizer and 10g steps (3)
The photic renovation agent of biomaterial pitch of gained, mix, mixture is then heated to 170 DEG C, stir 50min, shearing
160min, 30g stabilizer is added, it is agitated to produce pitch cementation of fissures cream.
Stabilizer used in the present embodiment is according to 1 by Sulfur and rubber powder：1 quality proportioning mixing.
The pitch cementation of fissures cream is poured into asphalt pavement crack, can be mended a split, when the pitch cementation of fissures cream of repair place fills
When there is crack, the solar irradiation 4h under the conditions of 5 DEG C, the free radical of fracture is excited to reconfigure, you can to fill pitch cementation of fissures cream
Selfreparing crack, so as to prevent crack from further expanding, realize preferable repair efficiency.
Embodiment 2
The photic renovation agent of biomaterial pitch of the present embodiment is made up of the raw material of following proportioning：
Its preparation method is same as Example 1.
It can be used for preparing pitch cementation of fissures cream with the above-mentioned photic renovation agent of biomaterial pitch, specific method is as follows：
900g matrix pitches are heated to 140 DEG C, line tapped oil that addition 250g subtracts three is as compatilizer and 10g steps (3)
The photic renovation agent of biomaterial pitch of gained, mix, mixture is then heated to 160 DEG C, stir 60min, shearing
170min, 20g stabilizer is added, it is agitated to produce pitch cementation of fissures cream.
Stabilizer used in the present embodiment is according to 2 by Sulfur and rubber powder：1 quality proportioning mixing.
The pitch cementation of fissures cream is poured into asphalt pavement crack, can be mended a split, when the pitch cementation of fissures cream of repair place fills
When there is crack, the solar irradiation 2h under the conditions of 40 DEG C, the free radical of fracture is excited to reconfigure, you can to fill pitch cementation of fissures cream
Selfreparing crack, so as to prevent crack from further expanding, realize preferable repair efficiency.
Embodiment 3
The photic renovation agent of biomaterial pitch of the present embodiment is made up of the raw material of following proportioning：
Its preparation method is same as Example 1.
The prepared photic renovation agent of biomaterial pitch can be used for preparing pitch cementation of fissures cream, specific method in aforementioned manners
It is as follows：
1100g matrix pitches are heated to 160 DEG C, line tapped oil mixing that addition 150g second line of distillation tapped oil and 200g subtract three
As the photic renovation agent of biomaterial pitch obtained by compatilizer, 10g steps (3), mix, be then heated to mixture
180 DEG C, 40min is stirred, 180min is sheared, adds 40g stabilizer, it is agitated to produce pitch cementation of fissures cream.
Stabilizer used in the present embodiment is according to 1.5 by Sulfur and rubber powder:1 quality proportioning mixing.
The pitch cementation of fissures cream is poured into asphalt pavement crack, can be mended a split, when the pitch cementation of fissures cream of repair place fills
When there is crack, the solar irradiation 4h under the conditions of 0 DEG C, the free radical of fracture is excited to reconfigure, you can to fill pitch cementation of fissures cream
Selfreparing crack, so as to prevent crack from further expanding, realize preferable repair efficiency.
Embodiment 4
The photic renovation agent of biomaterial pitch of the present embodiment is made up of the raw material of following proportioning：
The number-average molecular weight of the polyethylene glycol of the present embodiment is 380~420.
Its preparation method is same as Example 1.
The prepared photic renovation agent of biomaterial pitch can be used for preparing pitch cementation of fissures cream, specific method in aforementioned manners
It is as follows：
1000g matrix pitches are heated to 145 DEG C, add 280g second line of distillation tapped oil as compatilizer and 10g steps (3)
The photic renovation agent of biomaterial pitch of gained, mix, mixture is then heated to 175 DEG C, stir 45min, shearing
180min, 35g stabilizer is added, it is agitated to produce pitch cementation of fissures cream.
Stabilizer used in the present embodiment is according to 1.2 by Sulfur and rubber powder:1 quality proportioning mixing.
The pitch cementation of fissures cream is poured into asphalt pavement crack, can be mended a split, when the pitch cementation of fissures cream of repair place fills
When there is crack, the ultraviolet light 50min under the conditions of 5 DEG C, the free radical of fracture is excited to reconfigure, you can to make the pitch cementation of fissures
Cream fills selfreparing crack, so as to prevent crack from further expanding, realizes preferable repair efficiency.
Embodiment 5
The photic renovation agent of biomaterial pitch of the present embodiment is made up of following raw material proportioning：
Its preparation method is same as Example 1.
The prepared photic renovation agent of biomaterial pitch can be used for preparing pitch cementation of fissures cream, specific method in aforementioned manners
It is as follows：
950g matrix pitches are heated to 155 DEG C, add 320g second line of distillation tapped oil as compatilizer and 10g steps (3)
The photic renovation agent of biomaterial pitch of gained, mix, mixture is then heated to 180 DEG C, stir 50min, shearing
180min, 25g stabilizer is added, it is agitated to produce pitch cementation of fissures cream.
Stabilizer used in the present embodiment is according to 1.8 by Sulfur and rubber powder:1 quality proportioning mixing.
The pitch cementation of fissures cream is poured into asphalt pavement crack, can be mended a split, when the pitch cementation of fissures cream of repair place fills
When there is crack, the ultraviolet light 30min under the conditions of 40 DEG C, the free radical of fracture is excited to reconfigure, you can to fill pitch
Stitch cream and fill selfreparing crack, so as to prevent crack from further expanding, realize preferable repair efficiency.
Compatilizer in above-described embodiment 1~5 can also be by second line of distillation tapped oil and the line tapped oil that subtracts three according to arbitrarily matching somebody with somebody
Than made, and stabilizer be also can be by Sulfur and rubber powder according to 1~2:1 ratio mixes, can be by technology people
Member adjusts according to actual use.
In order to examine the photic renovation agent of the gained biomaterial pitch i.e. repairing effect of pitch cementation of fissures cream in the present invention, now lead to
Cross following verified：
1st, in order to examine influence of the renovation agent to asphalt performance obtained in the present invention, mixed respectively in matrix pitch
0.5%th, 1%, 2% renovation agent, using the performance of matrix pitch as compareing, influence of this renovation agent to asphalt performance is studied,
It is specific as follows：
(1) cryogenic property：Influence of this experiment renovation agent to pitch cryogenic property is characterized with 5 DEG C of ductilities, matrix pitch
And renovation agent volume is respectively 9.6cm, 9.8cm, 11.1cm, 11.9cm in 0.5%, 1%, 2% lower 5 DEG C of ductilities.Pitch is at 5 DEG C
Increase during ductility with the increase of renovation agent volume, the cryogenic property of pitch can be improved by illustrating the incorporation of renovation agent.
(2) workability：The workability of pitch is characterized with 135 DEG C of viscosity.Matrix pitch and renovation agent volume exist
0.5%th, 135 DEG C of viscosity under 1%, 2% are respectively 0.793Pa/s, 0.787Pa/s, 0.776Pa/s, 0.769Pa/s.Pitch
135 DEG C of viscosity reduced with the increase of renovation agent volume, illustrate the incorporation of renovation agent has necessarily to the workability of pitch
Improvement result.
(3) ageing properties：Ageing resistace index of the pitch under different renovation agent volumes is characterized with penetration ratio.Base
Matter pitch and the penetration ratio that renovation agent volume is 0.5%, 1%, 2% are respectively 74.8%, 75.1%, 75.9%, 76.5%.
Penetration ratio before and after ageing of asphalt increases with the increase of renovation agent volume.Illustrate ageing resistance of this renovation agent to pitch
Can be improved effect.
Thus cryogenic property of the photic renovation agent of biomaterial pitch to pitch obtained by the explanation present invention, application property
Energy, ageing resistace have some improvement.
2nd, the repairing effect of the pitch cementation of fissures cream prepared with the photic renovation agent of the biomaterial pitch
(1) bitumen samples process is prepared：Matrix pitch uses the pitch of Kelamayi 70, in order to exclude pitch self-healing property pair
The influence of pitch selfreparing effect, 5 DEG C of test ambient temperature.Under this test ambient temperature, pitch averagely splits after half an hour
Slit width degree does not change substantially.Pitch will be uniformly coated with slide, be drawn at pitch with small icking tool with crack.
(2) repair process：Pitch (sample one) with minute crack is repaired by the following method：This slide is placed on
Optical microphotograph Microscopic observation, read its initial average crack width；The gained pitch cementation of fissures cream of embodiment 1 is applied on crack,
Then 30min is irradiated under ultraviolet lamp in crack, obtains sample two；Gained Fig. 1 and Fig. 2, wherein, after Fig. 1 is interface failure
Pitch (sample one) optical microscope photograph, its average crack width is 375um after testing, and Fig. 2 is the pitch after repairing
The optical microscope photograph of (sample two), its average crack width is 175um after testing.
Pitch crack is obviously reduced it can be seen from Fig. 1 and Fig. 2 contrasts, and healing rate can illustrate this pitch to 53.3%
Cementation of fissures cream has the effect repaired well with selfreparing.
With above-mentioned identical test method to the photic renovation agent of biomaterial pitch obtained by other embodiments of the invention and drip
The repairing effect of blue or green cementation of fissures cream is verified that its result of the test is consistent with the result of above-described embodiment 1, is respectively provided with preferable reparation
Effect, and have improvement result to the performance of matrix pitch.
Claims (1)
1. following photic renovation agents of biomaterial pitch are preparing the application of pitch cementation of fissures cream：
Application of the above-mentioned photic renovation agent of biomaterial pitch in pitch cementation of fissures cream is prepared, its application method are as follows：
Pitch cementation of fissures cream is by quality parts ratio by the photic renovation agent of biomaterial pitch and compatilizer, stabilizer and matrix pitch
For 1：30：3：The raw material of 100 quality proportionings is made；
Above-mentioned compatilizer is second line of distillation tapped oil, and stabilizer is Sulfur and rubber powder according to 1：1 quality proportioning mixing；
The preparation method of above-mentioned pitch cementation of fissures cream is：Matrix pitch is heated to 150 DEG C, adds compatilizer and biomaterial pitch
Photic renovation agent, mix, be heated to 170 DEG C, stir 50min, shear 160min, add stabilizer, it is agitated to produce pitch filling
Stitch cream.
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| CN108840612B (en) * | 2018-07-25 | 2020-11-10 | 北京通途技术有限公司 | Preparation method of high-cohesiveness and high-strength pavement repairing material |
| CN110437638B (en) * | 2019-09-20 | 2021-03-30 | 长沙理工大学 | Asphalt modifier, modified asphalt and asphalt modification method |
| CN112194773B (en) * | 2020-10-13 | 2022-04-15 | 长安大学 | Dynamic diselenide bond polyurethane elastomer material and preparation method and application thereof |
| US20220243040A1 (en) * | 2021-01-29 | 2022-08-04 | Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College | Uv light activated self-healing asphalt binder and uses thereof |
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