CN115948121A - Modified asphalt coating based on mono-epoxy terminated diblock copolymer and preparation method and application thereof - Google Patents
Modified asphalt coating based on mono-epoxy terminated diblock copolymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a diblock copolymer modified asphalt coating based on a single epoxy end capping, a preparation method and an application thereof, wherein the modified asphalt coating comprises the following raw materials of asphalt, a plasticizer, a modifier and a ketimine latent curing agent, the modifier is a diblock copolymer of a single epoxy end capping, and the structural formula of the diblock copolymer of the single epoxy end capping is as follows:
wherein R is 1 Is C 1 ‑C 10 A is a polymer segment of a monoalkenyl arene, C is a polymer segment of butadiene and/or isoprene, R is 2 Is C 1 ‑C 12 Alkyl ethers of (a). The invention adopts the diblock copolymer with the single epoxy end capping as the modifier, can effectively reduce the preparation temperature of the modified asphalt coating, shorten the preparation time, reduce the energy consumption and effectively slow down the adverse consequences of degradation, coking, gelation and the like of the polymer in the high-temperature process. Meanwhile, the modified asphalt coating has low viscosity, can be constructed and applied at a lower temperature even at normal temperature, and solves the problems of complicated construction and smoke pollution existing in high-temperature construction of the coating.
Description
Technical Field
The invention relates to the technical field of building waterproof materials, in particular to a modified asphalt coating based on a mono-epoxy terminated diblock copolymer, and a preparation method and application thereof.
Background
The hot-melt rubber asphalt waterproof coating is prepared by taking asphalt, styrene thermoplastic elastomer and mineral powder as main materials, adding additives such as plasticizer, stabilizer and the like and mixing at high temperature, and has the advantages of high elongation, good adhesion and strong self-healing property. In engineering application, the hot-melt rubber asphalt waterproof coating is often used in a composite matching way with a waterproof coiled material, so that the problems of infirm bonding of lap joints, hollowing in a plane, gliding of a vertical surface, difficulty in operation of complex parts and the like of a single waterproof coiled material are solved, the influence on the waterproof coiled material caused by deformation of a base layer is eliminated, and the reliability and the durability of the waterproof layer are improved.
In the hot-melt rubber asphalt waterproof coating, styrene thermoplastic elastomers are dispersed in asphalt to form an aggregation structure and physical cross-linking points of styrene chain segments, so that the cohesion of the coating is provided, and the high-low temperature performance, the ageing resistance and the fatigue resistance of the asphalt coating are improved. However, in the preparation process of the hot-melt rubber asphalt waterproof coating, due to the existence of physical cross-linking points in the styrene structure, the elastomer needs to be swelled at high temperature for a long time to be dispersed in the matrix asphalt, and the swelling and dissolving process of the elastomer needs to consume a large amount of energy, and also causes the degradation and performance loss of the elastomer in the high-temperature process. In addition, due to the existence of physical cross-linking points of a styrene structure, the coating is sticky and colloidal, the cohesive force and the cohesive force are extremely strong, and the direct blade coating construction is difficult, so that a heating and melting method is mostly adopted, namely, the rubber asphalt waterproof coating is heated to a certain temperature by matched heating equipment and then has good fluidity, and then blade coating or spraying construction is carried out, but the construction difficulty is high and the energy consumption is high by utilizing the method.
Generally speaking, in the prior art, the application of the styrene thermoplastic elastomer in the preparation of the hot-melt rubber asphalt waterproof material cannot solve the contradiction between the physical mechanical property and the construction performance of the material. The addition amount of the elastomer is reduced, so that the viscosity of the rubber asphalt coating can be reduced, the workability can be improved, and the cohesion and the high-temperature resistance of the coating can be reduced; the increase of the addition amount of the elastomer can improve the cohesive force and the high temperature resistance of the coating, but also can cause the increase of the viscosity of the coating and the deterioration of the application performance. In addition, due to the physical crosslinking effect and the reinforcing effect of the styrene segment, the styrene-based thermoplastic elastomer also needs to swell at a high temperature for a long time to be dispersed in the asphalt, which is also a problem that cannot be overcome by the prior art.
Disclosure of Invention
The invention aims to solve the technical problem that the existing hot-melt rubber asphalt waterproof coating needs high-temperature treatment during preparation and application, so that energy loss is caused, and polymer is degraded and has performance loss and other adverse effects, and provides an improved modified asphalt coating.
The second purpose of the invention is to provide a preparation method of the modified asphalt coating.
The third purpose of the invention is to provide the application of the modified asphalt coating.
In order to achieve the purpose, the invention adopts the technical scheme that:
the modified asphalt coating comprises raw materials of asphalt, a plasticizer and a modifier, wherein the modifier is a mono-epoxy terminated diblock copolymer, and the structural formula of the mono-epoxy terminated diblock copolymer is as follows:
wherein R is 1 Is C 1 -C 10 A is a polymer segment of a monoalkenyl arene, C is a polymer segment of butadiene and/or isoprene, R is 2 Is C 1 -C 12 The modified asphalt coating also comprises a ketimine latent curing agent.
According to some embodiments of the invention, the mono alkenyl arene comprising a is selected from the group consisting of styrene, p-methylstyrene, p-tert-butylstyrene, 2, 4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene, vinylxylene, 1-diphenylethylene, and combinations of one or more thereof.
Preferably, the mono alkenyl arene is selected from the group consisting of styrene, p-methylstyrene, alpha-methylstyrene, in one or more combinations. More preferably, the mono alkenyl arene is styrene.
According to some embodiments of the invention, the R is 1 Is selected from C 1 -C 6 Alkyl group of (1). Preferably, said R is 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl. Further preferably, said R 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
According to some embodiments of the invention, the R is 2 Is selected from C 2 -C 8 Alkyl ethers of (a). Preferably, said R is 2 Is selected from methyl ethyl ether, methyl isopropyl ether, methyl butyl ether, methyl isobutyl ether, methyl amyl ether, methyl hexyl ether, diethyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl amyl ether and ethyl hexyl ether. Further preferably, said R 2 Selected from methyl ethyl ether, methyl isopropyl ether, diethyl ether and ethyl isopropyl ether.
According to some embodiments of the invention, the mono-epoxy terminated diblock copolymer is a mono-epoxy terminated styrene-butadiene/isoprene diblock copolymer.
According to some embodiments of the invention, the mass content of a in the mono-epoxy terminated diblock copolymer is from 10 to 50%, preferably from 20 to 40%. More preferably 25 to 35%.
According to some embodiments of the invention, the number average molecular weight of the mono-epoxy terminated diblock copolymer is 5000 to 150000, preferably 30000 to 80000, and more preferably 30000 to 50000.
According to some embodiments of the invention, the mass ratio of the asphalt, the monohydroxy-terminated diblock copolymer, the plasticizer, and the ketimine latent curing agent is 10: 0.05 to 0.5.
Further, the raw material of the modified asphalt coating also comprises a curing accelerator.
According to some embodiments of the present invention, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 5 to 30 parts of a mono-epoxy terminated diblock copolymer, 15 to 150 parts of a plasticizer, 0.5 to 5.0 parts of a ketimine latent curing agent, and 0.1 to 2 parts of a curing accelerator. Preferably, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 8-20 parts of a mono-epoxy-terminated diblock copolymer, 50-100 parts of a plasticizer, 1.0-4.0 parts of a ketimine latent curing agent and 0.2-1.0 part of a curing accelerator.
Further, the asphalt is base asphalt, such as 70# asphalt and 90# asphalt.
Further, the ketimine latent curing agent is prepared by reacting one or more of aliphatic amine, alicyclic amine, polyether amine and polyamide with ketone, such as commercially available ketimine DA315 and ketimine DA360A.
Further, the plasticizer is one or more of aromatic oil, naphthenic oil and paraffin oil.
Further, the curing accelerator is one or a combination of aniline accelerators and fatty amine accelerators, for example, the curing accelerator is one or a combination of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine and fatty amine.
According to some embodiments of the present invention, the raw material of the modified asphalt coating further comprises one or more of a reactive diluent, a filler, and a coupling agent.
According to some embodiments of the present invention, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 5-30 parts of a mono-epoxy terminated diblock copolymer, 15-150 parts of a plasticizer, 0.5-5.0 parts of a ketimine latent curing agent, 0.1-2 parts of a curing accelerator, 0-10 parts of a reactive diluent, 0-120 parts of a filler, and 0-5 parts of a coupling agent. Preferably, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 8-20 parts of a mono-epoxy-terminated diblock copolymer, 50-100 parts of a plasticizer, 1-2 parts of a ketimine latent curing agent, 0.1-2 parts of a curing accelerator, 0-10 parts of a reactive diluent, 0-120 parts of a filler and 0-5 parts of a coupling agent.
Further, the filler is one or a combination of more of talcum powder, heavy calcium, light calcium carbonate, kaolin, attapulgite, bentonite and silicon micropowder.
Further, the reactive diluent is one or more of a monoepoxy reactive diluent, a diepoxy reactive diluent and a polyepoxy reactive diluent.
Further, the coupling agent is a combination of one or more of gamma-aminopropyltriethoxysilane (KH 550), gamma- (2, 3-glycidoxy) propyltrimethoxysilane and gamma-methacryloxypropyltrimethoxysilane (KH 570).
The second technical scheme adopted by the invention is as follows: the preparation method of the modified asphalt coating comprises the following steps:
step S1, preparation of a mono-epoxy-terminated diblock copolymer
Anionically polymerizing the mono alkenyl arene monomers comprising a to form a polymer of mono alkenyl arene having activated ends;
polymerizing the polymer of mono alkenyl arene with activated ends and butadiene and/or isoprene to generate a diblock copolymer with activated ends;
reacting the diblock copolymer with activated ends with alkylene oxide and alkylogen oxide in sequence to obtain the copolymer with activated ends
A structural mono-epoxy terminated diblock copolymer;
step S2, preparing modified asphalt coating
And mixing all the raw materials of the modified asphalt coating to obtain the modified asphalt coating.
Further, the step S1 is implemented by:
step S11, in the presence of a saturated hydrocarbon solvent and an anionic polymerization initiator, reacting the mono alkenyl arene monomer to generate the polymer of the mono alkenyl arene with the activated end, so as to obtain a solution system containing the polymer of the mono alkenyl arene with the activated end;
step S12, adding butadiene and/or isoprene to the solution system containing the polymer of mono alkenyl arene with an activated end, and reacting the polymer of mono alkenyl arene with an activated end with butadiene and/or isoprene to generate the diblock copolymer with an activated end, so as to obtain a solution system containing the diblock copolymer with an activated end;
and S13, sequentially adding alkylene oxide and epoxy alkyl halide into a solution system containing the diblock copolymer with the activated end, and reacting the diblock copolymer with the activated end with the alkylene oxide and the epoxy alkyl halide to obtain the mono-epoxy-terminated diblock copolymer.
Further, the step S2 is implemented by:
step S21, mixing asphalt, a plasticizer and/or a filler, stirring and heating to 110-120 ℃ under the condition that the relative vacuum degree is-0.08-0.095 MPa, and dehydrating to obtain a first mixture;
s22, heating the first mixture to 140-160 ℃, adding the mono-epoxy terminated diblock copolymer, and dissolving the mono-epoxy terminated diblock copolymer to obtain a second mixture;
and S23, cooling the second mixture to 60-70 ℃, adding a ketimine latent curing agent, or/and adding one or a combination of more of a curing accelerator, a reactive diluent and a coupling agent, and mixing to obtain the modified asphalt coating.
In some embodiments, the saturated hydrocarbon solvent is at least one of pentane, octane, heptane, cyclohexane, n-hexane, benzene, toluene, ethylbenzene, xylene.
In some embodiments, the anionic polymerization initiator is an alkyl lithium initiator, the alkyl lithium initiator is one or a combination of RLi, R is an alkyl group having 1 to 10 carbon atoms, and Li is a lithium atom. Preferably, the alkyllithium initiator is selected from methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, hexyllithium, tert-octyllithium. Further preferably, the alkyllithium initiator is selected from the group consisting of methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, and tert-butyllithium.
In some embodiments, in step S11, the reaction is carried out at 40 to 60 ℃; in step S12, the reaction is carried out at 40-60 ℃; in step S13, the reactions with the alkylene oxide and the alkylogen oxide in sequence are respectively carried out at 40 to 60 ℃.
In some embodiments, the alkylene oxide is selected from the group consisting of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 2-pentylene oxide, hexylene oxide, and phenyl ethylene oxide.
In some embodiments, the epihalohydrin is selected from combinations of one or more of epichlorohydrin, epibromohydrin, and 1, 2-chloroepoxybutane.
The third technical scheme adopted by the invention is as follows: the waterproof material comprises a coating, wherein the coating is prepared from the modified asphalt coating or the modified asphalt coating prepared by the preparation method of the modified asphalt coating.
Further, the waterproof material may further include a modified asphalt waterproofing membrane disposed on at least one surface of the coating layer.
Furthermore, the modified asphalt waterproof coiled material is an elastomer modified asphalt waterproof coiled material, a plastomer modified asphalt waterproof coiled material or a self-adhesive polymer modified asphalt waterproof coiled material.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the modified asphalt coating disclosed by the invention adopts the mono-epoxy terminated diblock copolymer as the modifier, so that the preparation temperature of the modified asphalt coating can be effectively reduced, the preparation time is shortened, the energy loss is reduced, and the adverse effects of degradation, coking, gelation and the like of the polymer in a high-temperature process are effectively relieved. Meanwhile, the modified asphalt coating has low viscosity, can be constructed and applied at a lower temperature even at normal temperature, and solves the problems of complicated construction and smoke pollution existing in high-temperature construction of the coating.
The modified asphalt coating adopts the diblock copolymer with the end capped by the single epoxy as the modifier, and introduces the ketimine latent curing agent into the formula, and the ketimine latent curing agent can generate cross-linking reaction with epoxy groups in the modifier under the action of moisture in a base layer or air after construction, so that the triblock copolymer similar to SBS or SIS is formed in situ, certain cohesive strength and mechanical property are endowed to the modified asphalt coating, the application requirement of a waterproof material is met, and the service performance of a terminal product is not influenced.
Detailed Description
As described in the background art, the existing hot-melt rubber asphalt waterproof material modified by the styrene thermoplastic elastomer cannot solve the contradiction between the physical mechanical property and the construction property of the material, and the existing styrene thermoplastic elastomer has high dispersion temperature and long dispersion time.
According to the invention, the mono-epoxy terminated diblock copolymer is introduced into the modified asphalt coating as a modifier, an effective physical crosslinking point cannot be formed by using the aggregation state structure of the mono-epoxy terminated diblock copolymer, and compared with SBS or SIS, the modified asphalt coating has lower dissolution temperature and melt viscosity, so that the preparation temperature of the modified asphalt coating can be effectively reduced, the preparation time is shortened, the energy consumption is reduced, and adverse effects such as degradation, coking, gelation and the like of the polymer in a high-temperature process are effectively relieved. Meanwhile, because the aggregation structure of the mono-epoxy-terminated diblock copolymer cannot form an effective physical crosslinking point, the coating has low cohesive strength and low viscosity, can be constructed and applied at a low temperature even at normal temperature, and solves the problems of complicated construction and smoke pollution existing in high-temperature construction of the coating.
The invention introduces the ketimine latent curing agent into the formula, and the ketimine latent curing agent can generate cross-linking reaction with epoxy groups in the modifier under the action of moisture in a base layer or air after construction, so that triblock copolymer similar to SBS or SIS is formed in situ, and the service performance of a terminal product is not influenced.
The technical solutions of the present invention are described in detail below with reference to specific examples so that those skilled in the art can better understand and implement the technical solutions of the present invention, but the present invention is not limited to the scope of the examples.
Some of the raw material sources in the following examples:
asphalt: 70# asphalt, mao famous division of petrochemical company, ltd.
Active diluent: 1, 6-hexanediol diglycidyl ether, guangzhou, a new materials, inc; or epoxidized soybean oil, shenzhen Dongktian chemical Co., ltd.
Ketimine latent curing agent: DA315 or DA360A, viierna chemical ltd, guangzhou.
Curing accelerator: DMP30, guangzhou commercial enhancement chemical ltd; or, dodecylamine, shandonghao Shuihai chemical Co., ltd.
Silane coupling agent: KH550 or KH570, chemical agents limited of the national drug group.
Plasticizer: naphthenic oil.
Example 1
This example provides a mono-epoxy terminated styrene-butadiene diblock copolymer,
the preparation method comprises the following steps:
injecting 125g of cyclohexane solution containing 25g of styrene into a polymerization bottle (under the protection of nitrogen), adding 0.27g of tetrahydrofuran as an activating agent, slowly adding the cyclohexane solution of n-butyllithium by using a syringe for impurity breaking, quickly adding 1.5ml of effective n-butyllithium solution at 50 ℃ when the system is from colorless to faint yellow, wherein the molar concentration of the n-butyllithium solution is 1.2mol/L, and initiating polymerization for 30min to obtain a solution system of the polymer of the mono alkenyl arene with an activated end; then, 300g of cyclohexane solution containing 75g of butadiene is added at a time, and polymerization is carried out for 30min at 50 ℃ to obtain a solution system of the styrene-butadiene diblock copolymer with an activated end; finally, 1.0ml of ethylene oxide is added for reaction for 15min, 1.2ml of epichlorohydrin is added for reaction for 15min, and the reaction is stopped by 1.8ml of ethanol. And adding 1.5 mass percent of 264 anti-aging agent according to the mass of the final polymerization product. And after the polymerization is finished, the reaction product is subjected to rotary evaporation to remove the solvent, and then is dried in a vacuum box to obtain the mono-epoxy-terminated styrene-butadiene block copolymer. The mono-epoxy terminated styrene-butadiene block copolymer had a number average molecular weight of 56400 and a molecular weight distribution of 1.08 as determined by GPC.
Example 2
This example provides a mono-epoxy terminated styrene-butadiene diblock copolymer,
the preparation method specifically comprises the following steps:
injecting 175g of cyclohexane solution containing 35g of styrene into a polymerization bottle (under the protection of nitrogen), adding 0.11g of tetrahydrofuran as an activating agent, slowly adding the cyclohexane solution of n-butyllithium by using an injector to break impurities, quickly adding 0.6ml of effective n-butyllithium solution at 50 ℃ when the system is unchanged from colorless to light yellow, wherein the molar concentration of the n-butyllithium solution is 1.2mol/L, and initiating polymerization for 30min to obtain a solution system of the polymer of the mono alkenyl arene with an activated end; then, 260g of cyclohexane solution containing 65g of butadiene is added at a time, and polymerization is carried out for 30min at 50 ℃ to obtain a solution system of the styrene-butadiene diblock copolymer with the activated end; finally, 0.5ml of propylene oxide is added for reaction for 15min, 0.6ml of epichlorohydrin is added for reaction for 15min, and the reaction is stopped by 0.9ml of ethanol. And adding 1.5 mass percent of 264 antioxidant according to the mass of the final polymer product. And (3) after the polymerization is finished, performing rotary evaporation on the reaction product to remove the solvent, and then drying in a vacuum oven to obtain the mono-epoxy terminated styrene-butadiene block copolymer. The monoepoxy-terminated styrene-butadiene block copolymer had a number average molecular weight of 142500 and a molecular weight distribution of 1.10 as measured by GPC.
Example 3
This example provides a mono-epoxy terminated styrene-isoprene diblock copolymer,
the preparation method comprises the following steps:
injecting 125g of cyclohexane solution containing 25g of styrene into a polymerization bottle (under the protection of nitrogen), adding 0.36g of tetrahydrofuran as an activating agent, slowly adding the cyclohexane solution of n-butyllithium by using a syringe for impurity breaking, quickly adding 2.0ml of effective n-butyllithium solution at 50 ℃ when the system is unchanged from colorless to light yellow, wherein the molar concentration of the n-butyllithium solution is 1.2mol/L, and initiating polymerization for 30min to obtain a solution system of the polymer of the mono alkenyl arene with an activated end; then, adding 300g of cyclohexane solution containing 75g of isoprene at one time, and polymerizing for 30min at 50 ℃ to obtain a solution system of the styrene-isoprene diblock copolymer with an activated end; finally, 1.4ml of ethylene oxide is added for reaction for 15min, 1.6ml of epichlorohydrin is added for reaction for 15min, and the reaction is stopped by 2.4ml of ethanol. And adding 1.5 mass percent of 264 anti-aging agent according to the mass of the final polymerization product. And after the polymerization is finished, the reaction product is subjected to rotary evaporation to remove the solvent, and then is dried in a vacuum box to obtain the mono-epoxy-terminated styrene-isoprene block copolymer. The mono-epoxy terminated styrene-isoprene block copolymer had a number average molecular weight of 43500 and a molecular weight distribution of 1.06 as measured by GPC.
Example 4
This example provides a mono-epoxy terminated styrene-isoprene diblock copolymer,
the preparation method comprises the following steps:
injecting 175g of cyclohexane solution containing 35g of styrene into a polymerization bottle (under the protection of nitrogen), adding 0.90g of tetrahydrofuran as an activating agent, slowly adding the cyclohexane solution of n-butyllithium by using an injector to break impurities, quickly adding 5.0ml of effective n-butyllithium solution at 50 ℃ when the system is unchanged from colorless to light yellow, wherein the molar concentration of the n-butyllithium solution is 1.2mol/L, and initiating polymerization for 30min to obtain a solution system of the polymer of the mono alkenyl arene with an activated end; then, 240g of cyclohexane solution containing 65g of isoprene is added at a time, and polymerization is carried out for 30min at 50 ℃ to obtain a solution system of the styrene-isoprene diblock copolymer with an activated end; finally, 3.5ml of propylene oxide is added for reaction for 15min, 4.2ml of epichlorohydrin is added for reaction for 15min, and the reaction is stopped by 6.0ml of ethanol. And adding 1.5 mass percent of 264 anti-aging agent according to the mass of the final polymerization product. And (3) after the polymerization is finished, performing rotary evaporation on the reaction product to remove the solvent, and then drying in a vacuum oven to obtain the mono-epoxy terminated styrene-isoprene segmented copolymer. The monoepoxy-terminated styrene-butadiene block copolymer had a number average molecular weight of 18250 and a molecular weight distribution of 1.08 as measured by GPC.
Example 5
The modified asphalt coating provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 14 parts of a modifier (the styrene-butadiene diblock copolymer prepared in example 1), 80 parts of aromatic oil serving as a plasticizer, 315 parts of ketimine latent curing agent DA, 30 parts of curing accelerator DMP, 1 part of reactive diluent 1, 6-hexanediol diglycidyl ether, 40 parts of heavy calcium carbonate serving as a filler and 550.0 parts of coupling agent KH.
The preparation method comprises the following steps:
(1) Heating asphalt, plasticizer and filler to 95 ℃, mixing, stirring and heating to 115 ℃ under the condition that the relative vacuum degree is-0.09 MPa, and dehydrating for 3 hours to obtain a first mixture;
(2) Heating the first mixture to 140 ℃, adding a modifier, and after 2.5 hours, completely dissolving the modifier to obtain a second mixture;
(3) And cooling the second mixture to 60-70 ℃, adding the ketimine latent curing agent, the curing accelerator, the reactive diluent, the coupling agent and the like, and mixing and stirring uniformly to obtain the modified asphalt coating.
Example 6
The modified asphalt coating provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of No. 70 asphalt, 20 parts of a modifier (the styrene-butadiene diblock copolymer prepared in example 1), 100 parts of aromatic oil serving as a plasticizer, 315 parts of a ketimine latent curing agent DA, 30 parts of a curing accelerator DMP, 2 parts of a reactive diluent 1, 6-hexanediol diglycidyl ether, 50 parts of heavy calcium carbonate serving as a filler and 550 parts of a coupling agent KH.
The preparation method is the same as example 5.
Example 7
The modified asphalt coating provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of No. 70 asphalt, 8 parts of modifier (styrene-butadiene diblock copolymer prepared in example 1), 60 parts of plasticizer naphthenic oil, 315 parts of ketimine latent curing agent DA, 30 parts of curing accelerator DMP, 2 parts of reactive diluent 1, 6-hexanediol diglycidyl ether, 50 parts of filler calcium carbonate and 550 parts of coupling agent KH.
The preparation method is the same as example 5.
Example 8
The modified asphalt coating provided in this example is different from example 5 in that: the modifier was the styrene-butadiene diblock copolymer prepared in example 2, and the time for complete dissolution of the modifier in step (2) was 3.5h.
Example 9
The modified asphalt coating provided in this example is different from example 5 in that: the modifier was the styrene-isoprene diblock copolymer prepared in example 3, and the time for complete dissolution of the modifier in step (2) was 2.0h.
Example 10
The modified asphalt coating provided by the embodiment is different from the modified asphalt coating provided by the embodiment 5 in that: the modifier was the styrene-isoprene diblock copolymer prepared in example 4, and the time for complete dissolution of the modifier in step (2) was 1.0h.
Example 11
The modified asphalt coating provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of No. 70 asphalt, 20 parts of a modifier (the styrene-isoprene diblock copolymer prepared in example 4), 100 parts of plasticizer naphthenic oil, 315 parts of ketimine latent curing agent DA, and 30 parts of curing accelerator DMP.
Comparative example 1
The modified asphalt coating provided by the comparative example comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 14 parts of modifier (1301 SBS of ba ling petrochemical), 80 parts of plasticizer aromatic oil, 40 parts of filler heavy calcium and 550 parts of coupling agent KH.
The preparation method comprises the following steps:
heating 70# asphalt, a plasticizer and a filler to 160 ℃, stirring for melting, then adding a modifier, stirring at a shear rate of 400r/min, completely dissolving the modifier after 3 hours, then adding a coupling agent, stirring uniformly, cooling and discharging to obtain the modified asphalt coating.
Comparative example 2
The modified asphalt coating provided by the comparative example is different from that of comparative example 1 in that: the modifier is 1105SIS petrochemical in the country, and in the step (2), the dissolving time of the modifier is 3.5h.
The modified asphalt coatings of examples 5 to 11 and comparative examples 1 to 2 were tested for viscosity at 25 ℃ in accordance with GB/T10247-2008 "viscosity test method", and for heat resistance, low-temperature flexibility, water impermeability and adhesive strength in accordance with GB/T16777-2008 "test method for waterproof building coating" and JC/T852-1999 "solvent-based rubber asphalt waterproof coating", and the results are shown in Table 1.
Table 1 shows the results of the property tests of the modified asphalt coatings of examples 5 to 11 and comparative examples 1 to 2
The comparative examples 1 and 2 are solid at normal temperature, and the viscosity cannot be tested, and the paint cannot be applied at normal temperature, and can be applied only by heating. Examples 5 to 11 are all viscous liquids and can be used at room temperature. The result shows that the modified asphalt coating prepared by using the mono-epoxy terminated diblock copolymer as the modifier has the advantages of low cohesive strength and low viscosity, can be applied at low temperature and even normal temperature, and can solve the problems of complicated construction and smoke pollution existing in high-temperature construction of the coating because the aggregation structure of the modified asphalt coating can not form effective physical crosslinking points.
In addition, after the coating is subjected to film forming and maintenance according to GB/T16777-2008 'test method for building waterproof coatings', a coating with certain cohesive strength can be formed, and the ketimine latent curing agent is introduced into the formula and can be subjected to cross-linking reaction with an epoxy group in a modifier under the action of moisture in a base layer or air after construction, so that the coating is endowed with certain mechanical strength, the standard requirements of JC/T852-1999 'solvent type rubber asphalt waterproof coating' are met, and the final service performance of the coating can reach or even exceed the performance of a commercially available SBS or SIS modified asphalt coating.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (14)
1. The modified asphalt paint is prepared with asphalt, plasticizer and modifierCharacterized in that: the modifier is a mono-epoxy terminated diblock copolymer, wherein the structural formula of the mono-epoxy terminated diblock copolymer is as follows:
wherein R is 1 Is C 1 -C 10 A is a polymer segment of a monoalkenyl arene, C is a polymer segment of butadiene and/or isoprene, R 2 Is C 1 -C 12 The modified asphalt coating further comprises a ketimine latent curing agent.
2. The modified asphalt coating of claim 1, wherein: the mono alkenyl arene for forming the A is selected from one or a combination of more of styrene, p-methylstyrene, p-tert-butylstyrene, 2, 4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene, vinylxylene and 1, 1-diphenylethylene; and/or, said R 1 Is selected from C 1 -C 6 Alkyl groups of (a); and/or, said R 2 Is selected from C 2 -C 8 An alkyl ether of (2).
3. The modified asphalt coating according to claim 2, wherein: the mono alkenyl arene is selected from one or more of styrene, p-methylstyrene and alpha-methylstyrene; and/or the mono-epoxy terminated diblock copolymer is a mono-epoxy terminated styrene-butadiene/isoprene diblock copolymer.
4. The modified asphalt coating of claim 1, wherein: the mass content of the A in the mono-epoxy terminated diblock copolymer is 10-50%; and/or the number average molecular weight of the mono-epoxy terminated diblock copolymer is 5000 to 150000.
5. The modified asphalt coating of claim 4, wherein: the mass content of the A in the mono-epoxy end-capped diblock copolymer is 20-40%; and/or the number average molecular weight of the mono-epoxy terminated diblock copolymer is 30000-80000.
6. The modified asphalt coating material according to any one of claims 1 to 5, wherein: the mass ratio of the asphalt, the monohydroxy terminated diblock copolymer, the plasticizer and the ketimine latent curing agent is 10: 0.05 to 0.5.
7. The modified asphalt coating of claim 6, wherein: the raw materials of the modified asphalt coating also comprise a curing accelerator; and/or, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 5-30 parts of a mono-epoxy terminated diblock copolymer, 15-150 parts of a plasticizer, 0.5-5.0 parts of a ketimine latent curing agent and 0.1-2 parts of a curing accelerator.
8. The modified asphalt coating of claim 7, wherein: the modified asphalt coating comprises, by weight, 100 parts of asphalt, 8-20 parts of a mono-epoxy-terminated diblock copolymer, 50-100 parts of a plasticizer, 1.0-4.0 parts of a ketimine latent curing agent and 0.1-2 parts of a curing accelerator.
9. The modified asphalt coating of claim 7, wherein: the plasticizer is one or a combination of aromatic oil, naphthenic oil and paraffin oil; and/or the curing accelerator is one or more of 2,4, 6-tri (dimethylaminomethyl) phenol, triethanolamine and fatty amine; and/or the asphalt is base asphalt; and/or the raw materials of the modified asphalt coating also comprise one or the combination of more of a reactive diluent, a filler and a coupling agent.
10. A method for preparing a modified asphalt coating according to any one of claims 1 to 9, comprising the steps of:
step S1, preparation of a mono-epoxy-terminated diblock copolymer
Anionically polymerizing the mono alkenyl arene monomers comprising the a to form a polymer of mono alkenyl arene having activated ends;
polymerizing the mono alkenyl arene polymer with activated ends and butadiene and/or isoprene to generate a diblock copolymer with activated ends;
reacting the diblock copolymer with activated ends with an alkylene oxide and an epihalohydrin in sequence to obtain a copolymer with the activated ends
A structural mono-epoxy terminated diblock copolymer;
step S2, preparing the modified asphalt coating
And mixing all the raw materials of the modified asphalt coating to obtain the modified asphalt coating.
11. The method for preparing a modified asphalt paint according to claim 10, wherein the step S1 comprises:
step S11, in the presence of a saturated hydrocarbon solvent and an anionic polymerization initiator, reacting the mono alkenyl arene monomer to generate the polymer of the mono alkenyl arene with the activated end, so as to obtain a solution system containing the polymer of the mono alkenyl arene with the activated end;
step S12, adding butadiene and/or isoprene to the solution system containing the polymer of mono alkenyl arene with an activated end, and reacting the polymer of mono alkenyl arene with an activated end with butadiene and/or isoprene to generate the diblock copolymer with an activated end, so as to obtain a solution system containing the diblock copolymer with an activated end;
s13, sequentially adding alkylene oxide and epoxy alkyl halide into a solution system containing the diblock copolymer with the activated end, and reacting the diblock copolymer with the activated end with the alkylene oxide and the epoxy alkyl halide to obtain the mono-epoxy-terminated diblock copolymer; and/or the presence of a gas in the atmosphere,
the specific implementation of step S2 includes:
step S21, mixing asphalt, a plasticizer and/or a filler, stirring and heating to 110-120 ℃ under the condition that the relative vacuum degree is-0.08-0.095 MPa, and dehydrating to obtain a first mixture;
s22, heating the first mixture to 140-160 ℃, adding the mono-epoxy terminated diblock copolymer, and dissolving the mono-epoxy terminated diblock copolymer to obtain a second mixture;
and S23, cooling the second mixture to 60-70 ℃, adding a ketimine latent curing agent, or/and adding one or a combination of more of a curing accelerator, a reactive diluent and a coupling agent, and mixing to obtain the modified asphalt coating.
12. The method of preparing a modified asphalt coating according to claim 11, wherein: the saturated hydrocarbon solvent is at least one of pentane, octane, heptane, cyclohexane, normal hexane, benzene, toluene, ethylbenzene and xylene, the anion polymerization initiator is an alkyl lithium initiator, the alkyl lithium initiator is one or a combination of more of RLi, R is an alkane group with the carbon atom number of 1-10, and Li is a lithium atom; and/or the presence of a gas in the gas,
in step S11, the reaction is carried out at 40-60 ℃; in step S12, the reaction is carried out at 40-60 ℃; in step S13, the reactions with the alkylene oxide and the epoxy alkyl halide sequentially are respectively carried out at 40-60 ℃; and/or the presence of a gas in the atmosphere,
the alkylene oxide is selected from one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 2-pentylene oxide, hexylene oxide and phenyl ethylene oxide; and/or the presence of a gas in the gas,
the epoxy alkyl halide is one or more of epoxy chloropropane, epoxy bromopropane and 1, 2-epoxy chlorobutane.
13. A water resistant material comprising a coating characterized by: the coating layer is made of the modified asphalt coating material according to any one of claims 1 to 9 or the modified asphalt coating material prepared by the preparation method of the modified asphalt coating material according to any one of claims 10 to 12.
14. The waterproof material according to claim 13, characterized in that: the waterproof material may further include a modified asphalt waterproofing membrane disposed on at least one surface of the coating layer.
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