CN116813908A - Waterproof tackifying surface modifier for road steel slag and preparation method and application thereof - Google Patents
Waterproof tackifying surface modifier for road steel slag and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
- C04B18/141—Slags
- C04B18/142—Steelmaking slags, converter slags
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- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
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- C04B20/023—Chemical treatment
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
一种路用钢渣防水增粘表面改性剂及其制备方法与应用，其结构通式如下：通过疏水表面阻隔水分与钢渣中金属氧化物等活性成分的水化反应，抑制钢渣混合料在路面服役过程中的膨胀现象，且增强其与沥青结合料的粘结作用，进一步改善其路用性能，从而推动钢渣材料转化率与利用率的提升，实现工业固废的资源化利用。
A road steel slag waterproofing and thickening surface modifier and its preparation method and application. Its general structural formula is as follows: By blocking the hydration reaction between water and active components such as metal oxides in steel slag through the hydrophobic surface, the expansion of the steel slag mixture during pavement service is inhibited, and its bonding with the asphalt binder is enhanced to further improve its road performance. , thereby promoting the improvement of steel slag material conversion rate and utilization rate, and realizing the resource utilization of industrial solid waste.
Description
Technical Field
The invention belongs to the field of solid waste resource recycling and road construction materials, and particularly relates to a waterproof tackifying surface modifier for road steel slag, and a preparation method and application thereof.
Background
With the continuous perfection of the highway network in China, highway transportation has become the most common traffic mode in daily life, and meanwhile, the demand for high-quality road engineering materials is increasing. The pavement structure construction has huge consumption on natural stone, however, natural stone resources in China are increasingly pretty, partial provinces are continuously started to limit or even prohibit natural stone exploitation, and the adverse effects of environmental pollution, water and soil loss, ecological community destruction and the like caused by stone exploitation are serious. Under the contradiction, searching for a substitute of natural stone becomes a focus topic of road engineering, and a large amount of discarded industrial waste residues gradually enter the engineering field of view. The mechanical property of the steel slag is similar to that of rolled broken stone, so that the steel slag is hard, wear-resistant, good in particle shape and good in adhesion with asphalt, and has great potential of being applied to asphalt mixtures instead of aggregates. The strategy of 'double carbon' of green efficiency improvement and emission reduction and resource recycling is implemented in China, and the research of applying the steel slag to the asphalt pavement is developed under the environment of overlarge steel slag accumulation and scarcity of high-quality road building aggregates at present.
Unlike traditional road basalt and limestone macadam, the steel slag has rough surface and more pores after being subjected to smelting process, has stronger capability of absorbing liquid substances, contains f-CaO, f-MgO and the like with extremely high hydration activity, and if the steel slag component is not subjected to corresponding surface modification pretreatment, various metal oxide components in the steel slag are easy to generate hydration reaction in the road surface service process to form various hydration products and generate expansion phenomenon, so that the road surface structure is irrecoverably damaged. In addition, after rain water erodes, heavy metal ions in the steel slag permeate into surrounding soil along with runoff, so that local water resources and natural environment are endangered. Therefore, the steel slag material is popularized and applied in the field of pavement materials, and the primary problem is to solve the waterproof modification treatment of the surface of the steel slag material.
In summary, in order to meet the requirements of solid waste treatment and long-service life of road materials, it is imperative to develop waterproof tackifying surface modified steel slag materials, and the surface modified road steel slag with excellent water stability and adhesive property is promoted to more application scenes, which is the key to realize the 'double carbon' target in the traffic industry.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the defects of the prior art, the invention provides the waterproof tackifying surface modifier for the road steel slag, which inhibits the expansion phenomenon of the steel slag mixture in the service process of the road surface through hydration reaction of the water-repellent surface blocking water and active components such as metal oxides in the steel slag, enhances the bonding effect of the steel slag mixture and asphalt binder, and further improves the road performance, thereby promoting the improvement of the conversion rate and the utilization rate of the steel slag material and realizing the recycling utilization of industrial solid wastes.
The technical scheme is as follows: a waterproof tackifying surface modifier for road steel slag has the following structural general formula:wherein a=15 to 45, b=1 to 15, m=50 to 300, x=1 to 20, and a, b, m, x are integers; r1 and R2 are each independently selected from-OCH (CH) 3 )CH 2 -O-C 3 H 6 -、-OCH(CH 3 )CH 2 -O-C(＝O)-CH(CH 3 )CH 2 -、-OCH 2 CH(CH 3 )O-C(＝O)NH-(C 7 H 6 ) -any one of NHC (=o) -; r3 is selected from the group consisting of-NH (CH) 2 ) 3 Si(OC 2 H 5 ) 3 、-OCH(CH 3 )CH 2 O(CH 2 ) 3 Si(OCH 3 ) 3 、-CH 2 CH(CH 3 )C(＝O)O(CH 2 ) 3 Si(OCH 3 ) 3 、-NH(CH 2 ) 2 NH(CH 2 ) 3 Si(OC 2 H 5 ) 3 、-(CH 2 ) 8 Si(OC 2 H 5 ) 3 、-(CH 2 ) 2 Si(OC 2 H 4 OCH 3 ) 3 Any one of them; r' is selected from the group consisting of-NH (CH) 2 ) 2 NH-、-O(CH 2 ) 3 -O-C(＝O)C(＝O)CH 2 -、-NH(C 6 H 6 Cl)-CH 2 -(C 6 H 6 Cl) NH-.
The polymer repeating unit structure of the modifier is preferably as follows:
the preparation method of the waterproof tackifying surface modifier for the road steel slag comprises the following raw material components in parts by weight: hydrogen-containing silicone oil: 80-100 parts; tackifier: 10-31 parts; chain extender: 14-55 parts; curing agent: 15-25 parts; catalyst: 0.5-12 parts; inhibitors: 4-8 parts; the method comprises the following specific steps: (1) Heating the chain extender to 50-80 ℃ and preserving heat in an air or nitrogen environment; (2) Dropwise adding hydrogen-containing silicone oil into the chain extender in the step (1), sequentially adding a catalyst, an inhibitor and a tackifier after the dropwise adding is finished, stirring at 60-120 ℃ for reaction for 1.5-3 h, and distilling under reduced pressure to remove a solvent and unreacted substances after the reaction is finished; (3) And (3) adding a curing agent into the reaction product of the step (2), and fully reacting to obtain the catalyst.
The hydrogen-containing silicone oil is terminal hydrogen-containing silicone oil and/or double-terminal hydrogen-containing silicone oil; the tackifier comprises any one of gamma-aminopropyl triethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethyl (ethoxysilane, N-octyl triethoxysilane and vinyl-tri (2-methoxyethoxy) silane; the chain extender comprises at least one of allyl glycidyl ether, glycidyl methacrylate, toluene diisocyanate and polyether N220; the curing agent comprises any one of T-31 curing agent, 2-hydroxy-2-methyl propiophenone and 4,4' -methylenebis (2-chloroaniline).
The catalyst comprises any one of chloroplatinic acid, isopropanol solution of chloroplatinic acid, divinyl tetramethyl siloxane coordinated platinum catalyst, kanst catalyst and triphenylphosphine rhodium chloride; the inhibitor is isopropanol.
In the hydrogen-containing silicone oil, the hydrogen content is 0.4-1.6%, and the viscosity is 100-400 mPa.s.
In the step (2), hydrogen-containing silicone oil is added dropwise to the chain extender within 30-60 min.
The surface modifier is applied to waterproof tackifying modification of the steel slag surface.
The application steps are that the dried steel slag aggregate and the surface modifier are stirred and mixed, and then the water-proof tackifying modified steel slag is prepared after solidification, and the mass ratio of the steel slag aggregate to the surface modifier is (20-40): 1.
The above curing conditions are carried out according to the type of curing agent selected: curing for 12-24 h under the environment of 20-60 ℃ or ultraviolet curing for 1-3 min under a high-pressure mercury lamp.
The beneficial effects are that: (1) The invention introduces the chain extender component into the main chain of hydrogen-containing silicone oil with strong hydrophobicity and oleophobicity based on hydrosilylation reaction to prepare the modified polymethylhydrosiloxane which can be solidified under specific conditions, so that polysiloxane and polymeric chain extender form a two-phase polymeric network, the structural stability of the modifier is further improved, and a layer of compact waterproof film is formed on the surface of steel slag, thus playing a vital role in improving the volume stability of steel slag materials.
(2) The main component of the tackifier in the invention is a silane coupling agent, one end of the tackifier can react with chemical groups on the surface of inorganic matters, and the other end of the tackifier can be combined with high polymer materials, so that a bridge for stable adhesion is established between organic matters and inorganic matters with large performance differences. The silane coupling agent is introduced into the modified polymethylhydrosiloxane main chain, so that a chemical bond with higher strength can be formed at the steel slag-asphalt interface, the robustness of a hydrophobic interface is ensured, and a foundation is laid for long-acting service of the road steel slag aggregate in an actual operation environment.
(3) The hydrogen-containing silicone oil and the tackifier in the invention both contain siloxane components, and the organosilicon molecular film arranged outside the silicone oil and the tackifier in an oriented way has strong hydrophobicity and strong surface affinity, can react with hydrophilic groups-OH of steel slag materials, and endows the steel slag with hydrophobic capability after reducing the surface energy of the steel slag, thus being a key factor for realizing waterproof tackifying effect. The invention realizes the synergy of water resistance and adhesion by utilizing the coupling effect of water resistance bonding among multiple components and graft polymerization, and can maximize the improvement effect of the modifier on the surface performance of steel slag. The modified steel slag prepared by the invention can be used as a reliable aggregate in road pavement and bridge deck pavement mixture, and can show excellent road performance under different service conditions, so that the recycling of solid wastes such as steel slag can be promoted, and the method is more solid and one step towards achievement of a double-carbon target.
(4) The chain extender introduced in the invention comprises a system of curable epoxy, polyurethane and the like, has good compatibility with common polymer modified asphalt such as epoxy modified asphalt, polyurethane modified asphalt and the like, can ensure uniform mixing, full adhesion and uniform system of the surface modified steel slag and the high-performance asphalt cement, and is beneficial to popularization and application of waste steel slag in high-grade and high-performance paving surface materials.
Drawings
FIG. 1 shows the reaction mechanism for preparing a waterproof tackifying surface modifying agent according to example 2 of the present invention.
Fig. 2 is a schematic microscopic view of a coating film formed on the surface of a steel slag material by the waterproof tackifying surface modifying agent in the embodiment of the invention, wherein (a) is original untreated steel slag, and (b) is the waterproof tackifying surface modified steel slag prepared in the invention.
Detailed Description
The invention will be better understood from the following examples.
Example 1
The mass raw materials, manufacturers and parts by mass of each component are as follows:
table 1 example 1 raw materials conditions table of waterproof tackifying surface modifier
Under the catalytic action of chloroplatinic acid, the allyl glycidyl ether and hydrogen-containing silicone oil can undergo an addition reaction to form epoxy modified silicone oil, and form a cross-linked network structure through an epoxy group curing reaction, so that a stable water-blocking film is formed on the surface of the steel slag material, and the water stability of the steel slag material is improved.
The converter hot closed steel slag produced by Jiangsu permanent steel group Co-Ltd is adopted, and the specification is as follows: 1# (10-15 mm), 2# (5-10 mm), the specific technical indexes are shown in the following table 2:
table 2 example 1 steel slag material condition table
The waterproof tackifying surface modified steel slag of example 1 was prepared as follows:
(1) 16.8g of allyl glycidyl ether was charged into a three-necked round bottom flask equipped with a thermometer, stirrer, condensate reflux tube, and incubated at 100℃under nitrogen for 0.5h; (2) 120g of single-end hydrogen polydimethylsiloxane RH-H222-4 is dropwise added into the system through a constant pressure dropping funnel within 45min, 592 mu L of chloroplatinic acid, 4.8g of isopropanol and 37.2g of gamma-methacryloxypropyl trimethoxysilane are added into the system, the mixture is stirred and reacted for 3H at 110 ℃ for grafting, and the solvent and unreacted substances are removed by reduced pressure distillation for 0.5H; (3) After the liquid in the flask is clear and transparent, dropwise adding 30g T-31 curing agent to react for 0.5h to prepare the colorless transparent viscous waterproof tackifying modifier; (4) Adding the dried steel slag aggregate and the waterproof tackifying modifier into stirring equipment at 120 ℃ for continuous stirring for 3-5 min, filtering out the redundant modifier after the steel slag aggregate and the waterproof tackifying modifier are contained, and placing the steel slag into a 60 ℃ oven or a vacuum drying oven for curing for 24h to prepare the waterproof tackifying modified steel slag. Further, the mass ratio of the steel slag aggregate to the modifier in the step (4) is 25:1.
Example 1 waterproof tackifying surface modified steel slag properties are shown in table 3 below:
table 3 example 1 waterproof adhesion-promoting surface-modified Steel slag Water stability and adhesion Properties
Example 2
The mass raw materials, manufacturers and parts by mass of each component are as follows:
table 4 example 2 raw materials conditions table of waterproof tackifying surface modifier
The acrylated polysiloxane is one of the representative types of the ultraviolet light curing molding organic silicon material, and has the advantages of low energy consumption, high speed, easy operation and the like compared with the traditional heat curing technology. In the embodiment, ultraviolet light curing is completed by virtue of the photoinitiator effect of 2-hydroxy-2-methyl propiophenone, so that a compact crosslinked network structure on the steel slag surface is formed, and the steel slag has lasting hydrophobicity.
The steel slag material was the same as in example 1.
The waterproof tackifying surface modified steel slag of example 2 was prepared as follows:
(1) 82.5g of glycidyl methacrylate are introduced into a three-necked round bottom flask with thermometer, stirrer, condensate reflux tube; (2) 150g of hydrogen-terminated polydimethyl hydrogen siloxane RH-LHC-3 is added dropwise in 45min through a constant pressure dropping funnel, 592 mu L of chloroplatinic acid, 7.5g isopropanol and 45g gamma-methacryloxypropyl trimethoxysilane are added into the system, the mixture is stirred and reacted for 3h at 110 ℃ for grafting, and the solvent and unreacted substances are removed by reduced pressure distillation for 0.5h; (3) After the liquid in the flask is clear and transparent, 22.5g of 2-hydroxy-2-methyl propiophenone is dripped to react for 0.5h to prepare a colorless transparent viscous waterproof tackifying modifier, wherein the reaction mechanism is shown in figure 1; (4) Adding the dried steel slag aggregate and the waterproof tackifying modifier into stirring equipment at 60 ℃, continuously stirring for 3-5 min, filtering out the redundant modifier after the steel slag is contained, and placing the steel slag under a 2000W high-pressure mercury lamp at a distance of 20cm for ultraviolet curing for 60s to prepare the waterproof tackifying modified steel slag. Further, the mass ratio of the steel slag aggregate to the modifier in the step (4) is 25:1.
Example 2 waterproof tackifying surface modified steel slag properties are shown in table 5 below:
table 5 example 2 waterproof adhesion-promoting surface-modified Steel slag Water stability and adhesion Properties
Example 3
The mass raw materials, manufacturers and parts by mass of each component are as follows:
table 6 example 3 raw materials conditions table of waterproof tackifying surface modifier
The polyurethane modified organosilicon is formed by grafting and copolymerizing prepolymer formed by isocyanate and polyol and organosilicon, and compared with pure organosilicon resin and pure polyurethane, the modified material has a complex soft and hard segment microphase separation structure, and has great improvement on the performances of moisture resistance, thermal stability and the like. In addition, the small molecular silane coupling agent can be introduced to convert a small amount of isocyanate groups into hydrolyzable alkoxy silane groups, and has the modification effect of improving the cohesiveness and the water resistance of the moisture-cured polyurethane adhesive.
The steel slag material was the same as in example 1.
The waterproof tackifying surface modified steel slag of example 3 was prepared as follows: (1) 19.2g of polyether N220 is added into a three-neck round bottom flask with a thermometer, a stirrer and a condensing reflux pipe, is cooled to 55 ℃ after vacuum dehydration at 105 ℃, is introduced with nitrogen, 38.4g of toluene diisocyanate is added dropwise, the NCO/OH molar ratio is controlled to be 3.5, and the temperature is raised to 85 ℃ for reaction for 0.5h, so as to form a polyurethane prepolymer; (2) 128g of single-end hydrogen polydimethylsiloxane RH-H222-4 is dropwise added in 45min through a constant pressure dropping funnel, 395uL of chloroplatinic acid and 12.8g of isopropanol are added into the system, the NCO matrix content fraction is measured by a di-n-butylamine-toluene method, 16g of gamma-aminopropyl triethoxysilane is added when the NCO matrix content fraction is lower than 7.0%, the grafting is carried out by stirring reaction at 60 ℃ for 1.5H, and the solvent and unreacted substances are removed by reduced pressure distillation for 0.5H; (3) After the liquid in the flask is golden yellow, clear and transparent, heating to 110 ℃, dropwise adding 32g of 4,4' -methylenebis (2-chloroaniline), stirring and reacting for 0.5h, and preparing the waterproof tackifying modifier; (4) Adding the dried steel slag aggregate and the waterproof tackifying modifier into stirring equipment at 120 ℃, continuously stirring for 3-5 min, filtering out the redundant modifier after the stirring, and solidifying for 12h at normal temperature to prepare the waterproof tackifying modified steel slag. Further, the mass ratio of the steel slag aggregate to the modifier in the step (4) is 25:1.
Example 3 waterproof adhesion-promoting surface-modified steel slag properties are shown in table 7 below:
table 7 example 3 waterproof adhesion-promoting surface modified slag Water stability and adhesion Properties
Comparative example 1
The mass raw materials, manufacturers and parts by mass of each component are as follows:
table 8 comparative example 1 raw material cases table of surface modifier
The steel slag material was the same as in example 1.
The surface modified steel slag of comparative example 1 was prepared as follows:
(1) Adding pure KH-550 silane coupling agent into C 2 H 5 OH and H 2 Mixing the materials in O solution, wherein the mass ratio is KH-550:H 2 O:C 2 H 5 OH＝1:9:10；
(2) Stirring the mixed solution at 800rpm for 30min at 60 ℃ by using an electric stirrer, and preserving the temperature of the mixed solution in a 25 ℃ incubator for 40min after stirring;
(3) Soaking steel slag in KH-550 solution, filtering the steel slag after 40min, and placing the steel slag in a tray;
(4) Preserving the steel slag in a baking oven at 160 ℃ for 2 hours to solidify the silane coupling agent on the surface of the steel slag;
(5) And (3) preserving heat for 3 hours in a baking oven at 105 ℃ and drying to obtain the silane coupling agent modified steel slag.
Comparative example 1 modified steel slag properties are shown in table 9 below:
table 9 comparative example 1 modified steel slag Water stability and adhesion Properties
Comparative example 2
The mass raw materials, manufacturers and parts by mass of each component are as follows:
table 10 comparative example 2 raw material cases table of surface modifier
The steel slag material was the same as in example 1.
The surface modified steel slag of comparative example 2 was prepared as follows:
(1) Diluting the organosilicon water repellent and the dimethylbenzene according to the mass ratio of 2:1;
(2) Adding the xylene solution of the organosilicon water repellent into the steel slag according to the amount of 4% of the mass of the steel slag, and continuously stirring for 5-10 min to uniformly distribute the modifier solution on the surface of the steel slag;
(2) Placing the mixed modified steel slag into an oven, and curing for 1-2 h at 150 ℃;
(3) And after the steel slag surface modifier solution is completely solidified, taking out the steel slag from the oven, and cooling at room temperature to obtain the silicone resin modified steel slag.
Comparative example 2 modified steel slag properties are shown in table 11 below:
table 11 comparative example 2 modified steel slag water stability and adhesion Properties
Comparative example 3
Raw untreated steel slag materials are adopted, and the material technical indexes are the same as those of example 1.
Comparative example 3 steel slag properties are shown in table 12 below:
table 12 comparative example 3 steel slag water stability and adhesion properties
Examples 1-3 above all pertain to a waterproof tackifying surface modified steel slag in the present invention; comparative example 1 is a modified steel slag using only a silane coupling agent; comparative example 2 is modified steel slag using only silicone resin, and comparative example 3 is unmodified raw steel slag. The results of the water stability and adhesion performance tests are summarized in the following table:
table 13 summary of test results for water stability and adhesion properties of examples and comparative examples
From the above table data analysis, the following conclusions can be drawn:
(1) The water contact angles of the waterproof tackifying modified steel slag in examples 1-3 are 140.2 degrees, 134.8 degrees and 135.5 degrees respectively, which are far greater than 52.3 degrees of the raw steel slag in comparative example 3, are at the same level with the waterproof modified steel slag in comparative example 2, and the whole is better than that of the tackifying modified steel slag in comparative example 1, which indicates that the modifier can twist the hydrophilicity of the steel slag surface into hydrophobicity and prevent water damage invasion from the source;
(2) The water absorption and the volume expansion rate of the waterproof tackifying modified steel slag in the examples 1-3 are lower than those of the original steel slag in the comparative example 3, so that the water stability of the road steel slag aggregate is improved;
(3) Compared with the original steel slag in the comparative example 3, the residual porosity of the nitrogen adsorption and desorption method in the examples 1-3 is greatly reduced, which proves that the waterproof tackifying modifier can form a coating film with a certain thickness on the surface of the steel slag, and can block part of through pores and improve the surface closure of the steel slag material while filling most of micro-opening gaps;
(4) The adhesion grades of the steel slag-asphalt in examples 1-3 and comparative examples 1-2 reach 5, which shows that different modification methods have a certain improvement effect on the adhesion between the steel slag and the asphalt, but the influence of the different modification methods is difficult to quantify, the adhesion force of the steel slag-asphalt interface can show the gain degree of the adhesion effect of each modification method, and compared with the original steel slag in comparative example 3, the improvement range of the steel slag-asphalt adhesive in examples 1-3 is respectively improved by 66.3%, 76.0% and 59.0%, and is similar to that of comparative example 1, but is larger than that of the waterproof modified steel slag in comparative example 2, which shows that the waterproof adhesion-promoting modifier can further ensure the adhesion of the steel slag and the asphalt, and is beneficial to comprehensively improving the road performance of the steel slag asphalt mixture.
From the conclusion, the waterproof tackifying surface modified road steel slag is improved considerably in water stability and adhesive property, and the waterproof effect and the tackifying effect of the modifier are coupled due to the common structural characteristics of polysiloxane, so that the adhesion between the waterproof tackifying surface modified road steel slag and asphalt cement can be improved through the group affinity of the coupling agent while a stable hydrophobic film is formed on the surface of the steel slag, and the waterproof tackifying surface modified road steel slag has important significance for optimizing the performance of the road steel slag and recycling the waste steel slag.
The invention provides a road steel slag waterproof tackifying surface modifier, a preparation method and an application thought and a method thereof, and particularly the method and the method for realizing the technical scheme are numerous, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by those skilled in the art without departing from the principle of the invention, and the improvements and the modifications are also regarded as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (10)
1. The waterproof tackifying surface modifier for the road steel slag is characterized by having the following structural general formula:
wherein a=15 to 45, b=1 to 15, m=50 to 300, x=1 to 20, and a, b, m, x are integers; r1 and R2 are each independently selected from
-OCH(CH 3 )CH 2 -O-C 3 H 6 -、-OCH(CH 3 )CH 2 -O-C(＝O)-CH(CH 3 )CH 2 -、
-OCH 2 CH(CH 3 )O-C(＝O)NH-(C 7 H 6 ) -any one of NHC (=o) -; r3 is selected from
-NH(CH 2 ) 3 Si(OC 2 H 5 ) 3 、-OCH(CH 3 )CH 2 O(CH 2 ) 3 Si(OCH 3 ) 3 、
-CH 2 CH(CH 3 )C(＝O)O(CH 2 ) 3 Si(OCH 3 ) 3 、-NH(CH 2 ) 2 NH(CH 2 ) 3 Si(OC 2 H 5 ) 3 、-(CH 2 ) 8 Si(OC 2 H 5 ) 3 、
-(CH 2 ) 2 Si(OC 2 H 4 OCH 3 ) 3 Any one of them; r' is selected from the group consisting of-NH (CH) 2 ) 2 NH-、
-O(CH 2 ) 3 -O-C(＝O)C(＝O)CH 2 -、-NH(C 6 H 6 Cl)-CH 2 -(C 6 H 6 Cl) NH-.
2. The water-proof and tackifying surface modifier for road steel slag according to claim 1, wherein the polymer repeating unit structural formula of the modifier is preferably as follows:
3. the preparation method of the road steel slag waterproof tackifying surface modifier as claimed in claim 1 or 2, which is characterized by comprising the following raw material components in parts by weight: hydrogen-containing silicone oil: 80-100 parts; tackifier: 10-31 parts; chain extender: 14-55 parts; curing agent: 15-25 parts; catalyst: 0.5-12 parts; inhibitors: 4-8 parts; the method comprises the following specific steps: (1) Heating the chain extender to 50-80 ℃ and preserving heat in an air or nitrogen environment; (2) Dropwise adding hydrogen-containing silicone oil into the chain extender in the step (1), sequentially adding a catalyst, an inhibitor and a tackifier after the dropwise adding is finished, stirring at 60-120 ℃ for reaction for 1.5-3 h, and distilling under reduced pressure to remove a solvent and unreacted substances after the reaction is finished; (3) And (3) adding a curing agent into the reaction product of the step (2), and fully reacting to obtain the catalyst.
4. The method for preparing the steel slag waterproof tackifying surface modifier for roads according to claim 3, wherein the hydrogen-containing silicone oil is terminal side hydrogen-containing silicone oil and/or double end side hydrogen-containing silicone oil; the tackifier comprises any one of gamma-aminopropyl triethoxysilane, gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl trimethyl (ethoxysilane, N-octyl triethoxysilane and vinyl-tri (2-methoxyethoxy) silane; the chain extender comprises at least one of allyl glycidyl ether, glycidyl methacrylate, toluene diisocyanate and polyether N220; the curing agent comprises any one of T-31 curing agent, 2-hydroxy-2-methyl propiophenone and 4,4' -methylenebis (2-chloroaniline).
5. The method for preparing the steel slag waterproof tackifying surface modifier for roads according to claim 3, wherein the catalyst comprises any one of chloroplatinic acid, isopropanol solution of chloroplatinic acid, divinyl tetramethyl siloxane coordinated platinum catalyst, cassitter catalyst and triphenylphosphine rhodium chloride; the inhibitor is isopropanol.
6. The process for preparing a water-proof and viscosity-increasing surface modifier for road steel slag according to claim 4, wherein the hydrogen-containing silicone oil has a hydrogen content of 0.4-1.6% and a viscosity of 100-400 mPa.s.
7. The process for preparing a water-proof and viscosity-increasing surface modifier for road steel slag according to claim 3, wherein in the step (2), hydrogen-containing silicone oil is added dropwise to the chain extender within 30-60 min.
8. Use of the surface modifier according to claim 1 or 2 for waterproof tackifying modification of steel slag surfaces.
9. The method according to claim 8, wherein the step of mixing the dried steel slag aggregate with the surface modifier by stirring and then solidifying the mixture to obtain the waterproof tackifying modified steel slag, wherein the mass ratio of the steel slag aggregate to the surface modifier is (20-40): 1.
10. The use according to claim 8, wherein the curing conditions are carried out according to the type of curing agent selected: curing for 12-24 h under the environment of 20-60 ℃ or ultraviolet curing for 1-3 min under a high-pressure mercury lamp.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119504208A (en) * | 2025-01-23 | 2025-02-25 | 长安大学 | A solid waste-based cold-mix asphalt mixture for preventive maintenance and its preparation method and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399651A (en) * | 1994-05-10 | 1995-03-21 | Dow Corning Corporation | Adhesion promoting additives and low temperature curing organosiloxane compositions containing same |
| CN101585905A (en) * | 2009-07-06 | 2009-11-25 | 中国科学院广州化学研究所 | Organic silicon modified phenolic epoxy curing agent for copper-clad board of printed circuit and preparation method thereof |
| JP2011208120A (en) * | 2010-03-09 | 2011-10-20 | Momentive Performance Materials Inc | Self-adhesive polyorganosiloxane composition |
| CN102942326A (en) * | 2012-11-21 | 2013-02-27 | 武汉理工大学 | Organic silicon enhancer, renewable aggregate and bituminous mixture and applications |
| CN104744704A (en) * | 2015-03-04 | 2015-07-01 | 深圳新宙邦科技股份有限公司 | Tackifying and reinforcing modified polysiloxane and preparation method and application thereof |
| CN111363103A (en) * | 2020-03-27 | 2020-07-03 | 无锡市百合花胶粘剂厂有限公司 | Preparation method of tackifier for addition type organic silicon adhesive |
| CN113105864A (en) * | 2021-03-01 | 2021-07-13 | 华南理工大学 | Epoxy modified organic silicon gel and preparation method and application thereof |
| CN113501961A (en) * | 2021-07-26 | 2021-10-15 | 浙江励德有机硅材料有限公司 | Tackifier, self-adhesive two-component addition type organic silicon pouring sealant prepared from tackifier and preparation method of self-adhesive two-component addition type organic silicon pouring sealant |
-
2023
- 2023-06-26 CN CN202310763108.5A patent/CN116813908A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399651A (en) * | 1994-05-10 | 1995-03-21 | Dow Corning Corporation | Adhesion promoting additives and low temperature curing organosiloxane compositions containing same |
| CN101585905A (en) * | 2009-07-06 | 2009-11-25 | 中国科学院广州化学研究所 | Organic silicon modified phenolic epoxy curing agent for copper-clad board of printed circuit and preparation method thereof |
| JP2011208120A (en) * | 2010-03-09 | 2011-10-20 | Momentive Performance Materials Inc | Self-adhesive polyorganosiloxane composition |
| CN102942326A (en) * | 2012-11-21 | 2013-02-27 | 武汉理工大学 | Organic silicon enhancer, renewable aggregate and bituminous mixture and applications |
| CN104744704A (en) * | 2015-03-04 | 2015-07-01 | 深圳新宙邦科技股份有限公司 | Tackifying and reinforcing modified polysiloxane and preparation method and application thereof |
| CN111363103A (en) * | 2020-03-27 | 2020-07-03 | 无锡市百合花胶粘剂厂有限公司 | Preparation method of tackifier for addition type organic silicon adhesive |
| CN113105864A (en) * | 2021-03-01 | 2021-07-13 | 华南理工大学 | Epoxy modified organic silicon gel and preparation method and application thereof |
| CN113501961A (en) * | 2021-07-26 | 2021-10-15 | 浙江励德有机硅材料有限公司 | Tackifier, self-adhesive two-component addition type organic silicon pouring sealant prepared from tackifier and preparation method of self-adhesive two-component addition type organic silicon pouring sealant |
Non-Patent Citations (1)
| Title |
|---|
| 张凯等: ""高粘接性有机硅增粘剂的合成与应用"", 《热固性树脂》, vol. 37, no. 6, 30 November 2022 (2022-11-30), pages 24 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119504208A (en) * | 2025-01-23 | 2025-02-25 | 长安大学 | A solid waste-based cold-mix asphalt mixture for preventive maintenance and its preparation method and application |
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