Disclosure of Invention
The invention aims to solve the technical problems that the existing hot-melt rubber asphalt waterproof paint needs high-temperature treatment in preparation and application to cause energy loss, and the polymer generates adverse effects such as degradation, coking, gelation, adhesion loss and the like, so as to provide an improved modified asphalt paint.
The second object of the invention is to provide a preparation method of the modified asphalt paint.
A third object of the present invention is to provide a waterproof material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the raw materials of the modified asphalt coating comprise asphalt, a plasticizer and a modifier, wherein the modifier is a monohydroxy end-capped diblock copolymer, and the monohydroxy end-capped diblock copolymer has the structural formula: r is R1 -A-B-R2 -OH, wherein R1 Is C1 -C10 Wherein A is a monoalkenyl arene polymer segment, B is a butadiene and/or isoprene polymer segment, R2 Is C1 -C8 Alkyl of (a);
the modified asphalt coating also includes a polyisocyanate.
According to some embodiments of the invention, the mono alkenyl arene constituting the a is selected from the group consisting of one or more of styrene, p-methylstyrene, p-tert-butylstyrene, 2, 4-dimethylstyrene, a-methylstyrene, vinylnaphthalene, vinyltoluene, vinylxylene, 1-diphenylethylene.
Preferably, the mono alkenyl arene is selected from the group consisting of one or more of styrene, p-methylstyrene, alpha-methylstyrene. More preferably, the mono alkenyl arene is styrene.
The mono alkenyl arene is selected from one or a combination of more of styrene, p-methyl styrene and alpha-methyl styrene; and/or the monohydroxy-terminated diblock copolymer is a monohydroxy-terminated styrene-butadiene/isoprene diblock copolymer.
According to some embodiments of the invention, the R1 Selected from C1 -C6 Is a hydrocarbon group. Preferably, said R1 Selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl. Further preferably, the R1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl.
According to some embodiments of the invention, the R2 Selected from C2 -C6 Is a hydrocarbon group. Preferably, said R2 Selected from ethylene, propylene, isopropylene, butylene, isobutylene, pentylene, hexylene. Further preferably, the R2 Selected from the group consisting of methylene, ethylene, propylene, isopropylene, butylene, isobutylene, hexylene.
According to some embodiments of the invention, the mass content of a in the monohydroxy terminated diblock copolymer is 10-50%, preferably 20-40%, more preferably 25-35%.
According to some embodiments of the invention, the number average molecular weight of the monohydroxy terminated diblock copolymer is from 5000 to 150000, preferably from 30000 to 80000.
According to some embodiments of the invention, the polyisocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, and modified diphenylmethane diisocyanate, isophorone diisocyanate, 1, 6-hexamethylene diisocyanate.
According to some embodiments of the invention, the plasticizer is a combination of one or more of aromatic, naphthenic, and paraffinic oils.
According to some embodiments of the invention, the asphalt is a base asphalt, such as 70# asphalt, 90# asphalt.
According to some embodiments of the invention, the mass ratio of the asphalt, the plasticizer, the modifier and the polyisocyanate is 10:1.5-15:0.5-3.0:0.05-0.3. Preferably, the mass ratio of the asphalt to the plasticizer to the modifier to the polyisocyanate is 10:5-12:0.8-2.0:0.08-0.2.
In some embodiments, the feedstock for the modified asphalt coating further comprises a catalyst. The catalyst is one or a combination of a plurality of dibutyl tin dilaurate, stannous octoate, dibutyl tin diacetate, dibutyl tin (dodecyl sulfide) and dibutyl tin dichloride.
In some embodiments, the modified asphalt coating comprises, by weight, 100 parts of asphalt, 15-150 parts of plasticizer, 5-30 parts of modifier, 0.5-3 parts of polyisocyanate, and 0.1-0.6 part of catalyst.
In some embodiments, the raw materials of the modified asphalt coating further comprise at least one of a filler, a defoamer, a dispersant, a leveling agent, an anti-settling agent, a coupling agent and an antioxidant.
Further, the filler is one or a combination of more of talcum powder, heavy calcium carbonate, light calcium carbonate, kaolin, attapulgite, bentonite and silicon micropowder.
The second technical scheme adopted by the invention is as follows: the preparation method of the modified asphalt paint comprises the following steps:
step S1, preparation of monohydroxy-terminated diblock copolymer
Subjecting the monoalkenyl arene monomer constituting the A to anionic polymerization to produce a monoalkenyl arene polymer having an activated end;
polymerizing the polymer of mono alkenyl arene having an activated end with butadiene and/or isoprene to produce a diblock copolymer having an activated end;
reacting the diblock copolymer having an activated end with an alkylene oxide, and then adding an acid to perform an acidification reaction to obtain the polymer having the R1 -A-B-R2 Monohydroxy-terminated diblock copolymers of the OH structure.
S2, preparing modified asphalt paint
And mixing all raw materials of the modified asphalt coating, and reacting the polyisocyanate with the modifier to obtain the modified asphalt coating.
According to some embodiments of the invention, the implementation of step S1 comprises: step S11, in the presence of a saturated hydrocarbon solvent and an anionic polymerization initiator, enabling the mono-alkenyl arene monomer to react to generate the mono-alkenyl arene polymer with an activated end, so as to obtain a solution system containing the mono-alkenyl arene polymer with the activated end;
step S12, adding butadiene and/or isoprene to a solution system containing the mono alkenyl arene polymer with the activated end, and enabling the mono alkenyl arene polymer with the activated end to react with butadiene and/or isoprene to generate the diblock copolymer with the activated end, so as to obtain a solution system containing the diblock copolymer with the activated end;
and S13, adding alkylene oxide into a solution system containing the diblock copolymer with the activated end, enabling the diblock copolymer with the activated end to react with the alkylene oxide, and then adding acid to carry out acidification reaction to obtain the monohydroxy-terminated diblock copolymer.
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, wherein the alkyl lithium initiator is selected from one or a combination of several of RLi, R is an alkyl group with 1-10 carbon atoms, and Li is a lithium atom. Preferably, the alkyl lithium initiator is selected from the group consisting of methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, amyl lithium, hexyl lithium, tert-octyl lithium. Further preferably, the alkyllithium initiator is selected from the group consisting of methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium.
In some embodiments, in step S11, the reaction is performed at 40-60 ℃; and/or, in the step S12, the reaction is carried out at 40-60 ℃; in the step S13, the reaction with alkylene oxide is performed at 40-60 ℃, and the acidification reaction is performed at 40-60 ℃.
In some embodiments, the alkylene oxide is one or a combination of more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 2-pentane oxide, hexane oxide, phenyl ethylene oxide.
In some embodiments, the acid is hydrochloric acid, and the mass concentration of the hydrochloric acid is 25-40 wt%.
According to some embodiments of the invention, the implementation of step S2 comprises:
step S21, mixing asphalt, plasticizer and/or filler, stirring and heating to 110-120 ℃ under the condition that the relative vacuum degree is minus 0.08-minus 0.095MPa, and dehydrating to obtain a first mixture;
step S22, heating the first mixture to 140-160 ℃, and adding the modifier to dissolve the modifier to obtain a second mixture;
and S23, cooling the second mixture to 80-85 ℃, adding the polyisocyanate to enable the polyisocyanate to react with the modifier, cooling to 60-70 ℃, and then adding a catalyst or/and one or a combination of a plurality of defoamer, dispersing agent, flatting agent, anti-settling agent, coupling agent and antioxidant, and mixing to obtain the modified asphalt coating.
The third technical scheme adopted by the invention is as follows: a waterproof material comprises a coating, wherein the coating is prepared from the modified asphalt paint or the modified asphalt paint prepared by the preparation method of the modified asphalt paint.
Further, the waterproof material is a composite material, and the composite material further comprises a modified asphalt waterproof coiled material arranged on at least one surface of the coating.
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 monohydroxy-terminated diblock copolymer as the modifier, has lower dissolution temperature and melt viscosity compared with SBS or SIS, can effectively reduce the preparation temperature of the modified asphalt coating, shortens the preparation time, reduces the energy consumption, and effectively reduces the adverse consequences of degradation, coking, gel and the like of the polymer in the high-temperature process. Meanwhile, the modified asphalt paint has smaller viscosity, can be applied in construction at lower temperature and even normal temperature, and solves the problems of complex construction and smoke pollution existing in high-temperature construction of the paint.
The modified asphalt coating adopts the monohydroxy-terminated diblock copolymer as the modifier, and polyisocyanate is introduced into the formula to react with the modifier to form the isocyanate-terminated diblock copolymer, and after construction, the isocyanate-terminated diblock copolymer can undergo a crosslinking reaction under the action of moisture in a base layer or air to form a triblock copolymer similar to SBS or SIS in situ, so that the modified asphalt coating is endowed with certain cohesive strength and mechanical property, 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 styrene thermoplastic elastomer modified hot-melt rubber asphalt waterproof material cannot solve the contradiction between the physical and mechanical properties and the construction properties of the material, and the existing styrene thermoplastic elastomer has high dispersion temperature and long time.
According to the invention, the monohydroxy-terminated diblock copolymer is introduced into the modified asphalt paint as a modifier, and an effective physical crosslinking point cannot be formed by utilizing the aggregation state structure of the monohydroxy-terminated diblock copolymer, so that the preparation temperature of the modified asphalt paint can be effectively reduced, the preparation time is shortened, the energy consumption is reduced, and adverse effects of degradation, coking, gel and the like of the polymer in a high-temperature process can be effectively alleviated. Meanwhile, as the aggregation state structure of the monohydroxy-terminated diblock copolymer cannot form an effective physical crosslinking point, the cohesive strength of the coating is lower, the viscosity is lower, the coating can be applied in construction at lower temperature even normal temperature, and the problems of complex construction and smoke pollution existing in high-temperature construction of the coating are solved.
The invention introduces polyisocyanate into the formula at the same time, and the polyisocyanate reacts with the monohydroxy end-capped diblock copolymer in the preparation process to form an isocyanate end-capped diblock copolymer structure, and after construction, the polyisocyanate can undergo a crosslinking reaction under the action of moisture in a base layer or air to form a triblock copolymer similar to SBS or SIS in situ, thereby endowing asphalt paint with certain cohesive strength, meeting the application requirements of waterproof paint and not affecting the service performance of terminal products.
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention, but is not intended to limit the scope of the present invention.
Example 1
The monohydroxy-terminated styrene-butadiene diblock copolymer provided in this example,
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 into the polymerization bottle by using a syringe to break impurities, rapidly adding 1.5ml of effective n-butyllithium solution after the system is unchanged from colorless to pale yellow at 50 ℃, initiating polymerization for 30min, and obtaining a solution system of the polymer of mono alkenyl arene with an activated end; then, 300g of a cyclohexane solution containing 75g of butadiene was added at a time and polymerized at 50℃for 30 minutes to obtain a solution system of a styrene-butadiene diblock copolymer having an activated end; finally, 2.1mL of ethylene oxide was added and reacted for 15min, acidified with 7.5mL of dilute hydrochloric acid (concentration 31.5 wt%) and added with 264 anti-aging agent in a mass percentage of 1.5% based on the mass of the final polymer product. And after the polymerization is finished, the reaction product is distilled off to remove the solvent, and then the reaction product is dried in a vacuum box, so that the monohydroxy-terminated styrene-butadiene segmented copolymer is obtained. GPC measured that the monohydroxy-terminated styrene-butadiene block copolymer had a number average molecular weight of 55640 and a molecular weight distribution of 1.05.
Example 2
The monohydroxy-terminated styrene-butadiene diblock copolymer provided in this example,
the preparation method comprises the following steps:
adding 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 into the polymerization bottle by using a syringe to break impurities, rapidly adding 0.6ml of effective n-butyllithium solution after the system is unchanged from colorless to pale yellow at 50 ℃, initiating polymerization for 30min, and obtaining a solution system of the polymer of mono alkenyl arene with an activated end; then, 260g of a cyclohexane solution containing 65g of butadiene was added at a time and polymerized at 50℃for 30 minutes to obtain a solution system of a styrene-butadiene diblock copolymer having an activated end; finally, 0.9mL of propylene oxide was added and reacted for 15min, acidified with 3mL of dilute hydrochloric acid (concentration 31.5 wt%) and 264 anti-aging agent was added in a mass percentage of 1.5% based on the mass of the final polymerization product. And after the polymerization is finished, the reaction product is distilled off to remove the solvent, and then the reaction product is dried in a vacuum box, so that the monohydroxy-terminated styrene-butadiene segmented copolymer is obtained. GPC measured that the monohydroxy-terminated styrene-butadiene block copolymer had a number average molecular weight of 138500 and a molecular weight distribution of 1.03.
Example 3
The monohydroxy-terminated styrene-isoprene diblock copolymer provided in this example,
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 into the polymerization bottle by using a syringe to break impurities, rapidly adding 2.0ml of effective n-butyllithium solution after the system is unchanged from colorless to pale yellow at 50 ℃, initiating polymerization for 30min, and obtaining a solution system of the polymer of mono alkenyl arene with an activated end; then, 300g of a cyclohexane solution containing 75g of isoprene was added at a time and polymerized at 50℃for 30 minutes to obtain a solution system of a styrene-isoprene diblock copolymer having an activated end; finally, 2.8mL of ethylene oxide was added and reacted for 15min, acidified with 10.0mL of dilute hydrochloric acid (concentration 31.5 wt%) and added with 264 anti-aging agent in a mass percentage of 1.5% based on the mass of the final polymer product. And after the polymerization is finished, the reaction product is distilled off to remove the solvent, and then the reaction product is dried in a vacuum box, so that the monohydroxy-terminated styrene-isoprene segmented copolymer is obtained. GPC measured that the monohydroxy-terminated styrene-isoprene block copolymer had a number average molecular weight of 42600 and a molecular weight distribution of 1.04.
Example 4
The monohydroxy-terminated styrene-isoprene diblock copolymer provided in this example,
the preparation method comprises the following steps:
adding 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 into the polymerization bottle by using a syringe to break impurities, rapidly adding 5.0ml of effective n-butyllithium solution after the system is unchanged from colorless to pale yellow at 50 ℃, initiating polymerization for 30min, and obtaining a solution system of the polymer of mono alkenyl arene with an activated end; then, 240g of a cyclohexane solution containing 65g of isoprene was added at a time and polymerized at 50℃for 30 minutes to obtain a solution system of a styrene-isoprene diblock copolymer having an activated end; finally, 7.0mL of propylene oxide was added and reacted for 15min, acidified with 25mL of dilute hydrochloric acid (concentration 31.5 wt%) and 264 anti-aging agent was added in a mass percentage of 1.5% based on the mass of the final polymer product. And after the polymerization is finished, the reaction product is distilled off to remove the solvent, and then the reaction product is dried in a vacuum box, so that the monohydroxy-terminated styrene-isoprene segmented copolymer is obtained. GPC measured that the monohydroxy-terminated styrene-butadiene block copolymer had a number average molecular weight of 16720 and a molecular weight distribution of 1.05.
Example 5
The modified asphalt paint provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 14 parts of modifier (styrene-butadiene diblock copolymer prepared in example 1), 80 parts of aromatic oil, 1.4 parts of isophorone diisocyanate, 0.28 part of stannous octoate, 40 parts of heavy calcium carbonate and 550 parts of coupling agent KH.
The preparation method comprises the following steps:
(1) Heating 70# asphalt, aromatic hydrocarbon oil and heavy calcium to 95 ℃, mixing, stirring and heating to 115 ℃ under the condition of the relative vacuum degree of-0.08 MPa, and dehydrating to obtain a first mixture;
(2) Heating the first mixture to 140 ℃, adding the modifier, and after 1.5 hours, completely dissolving the modifier to obtain a second mixture;
(3) And cooling the second mixture to 80 ℃, then adding isophorone diisocyanate to enable isophorone diisocyanate to react with a modifier, then cooling to 65 ℃, then adding stannous octoate and a coupling agent, and mixing to obtain the modified asphalt coating.
Example 6
The modified asphalt paint provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 8 parts of modifier (styrene-butadiene diblock copolymer prepared in example 1), 60 parts of naphthenic oil, 0.8 part of isophorone diisocyanate, 0.16 part of stannous octoate, 40 parts of heavy calcium carbonate, 550 parts of coupling agent KH 1 and 5 parts of solvent trimethylbenzene.
The preparation method is the same as in example 5.
Example 7
The modified asphalt paint provided in this example comprises, by weight, 100 parts of 70# asphalt, 20 parts of a modifier (styrene-butadiene diblock copolymer prepared in example 1), 120 parts of naphthenic oil, 2 parts of isophorone diisocyanate, 0.4 part of stannous octoate, 40 parts of heavy calcium, 550 parts of a coupling agent KH, and 0.5 part of a polysiloxane defoamer.
The preparation method is the same as in example 5.
Example 8
The modified asphalt paint provided in this example is different from that in example 5 in that: the modifier is the styrene-butadiene diblock copolymer prepared in example 2, and in step (2), the time for complete dissolution of the modifier is 2.5 hours.
Example 9
The modified asphalt paint provided in this example is different from that in example 5 in that: the modifier was a styrene-isoprene diblock copolymer prepared in example 3, and in step (2), the time for complete dissolution of the modifier was 1h.
Example 10
The modified asphalt paint provided in this example is different from that in example 5 in that: the modifier was a styrene-isoprene diblock copolymer prepared in example 4, and in step (2), the time for complete dissolution of the modifier was 30min.
Example 11
The modified asphalt paint provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 12 parts of modifier (styrene-butadiene diblock copolymer prepared in example 1), 80 parts of naphthenic oil, 1.2 parts of isophorone diisocyanate and 0.12 part of stannous octoate.
Comparative example 1
The modified asphalt paint provided by the comparative example comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 14 parts of modifier (Baling petrochemical 1301 SBS), 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, plasticizer and filler to 160 ℃, stirring and melting, then adding modifier, stirring at a shear rate of 400r/min, completely dissolving the modifier after 3 hours, then adding coupling agent, stirring uniformly, cooling and discharging to obtain the modified asphalt coating.
Comparative example 2
The modified asphalt paint provided in this comparative example is different from comparative example 1 in that: the modifier is 1105SIS which is petrochemical by Baling, and the dissolution time of the modifier in the step (2) is 3.5h.
Modified asphalt coatings of examples 5 to 11 and comparative examples 1 to 2 were tested according to GB/T10247-2008 viscosity test method 25o The viscosity of C was measured according to GB/T16777-2008 "building waterproof paint Experimental method" and JC/T852-1999 "solvent type rubber asphalt waterproof paint", and the heat resistance, flexibility at low temperature, water impermeability and adhesive strength were measured, and the results are shown in Table 1.
Table 1 shows the results of performance test of the modified asphalt paints of examples 5 to 11 and comparative examples 1 to 2
Wherein, comparative example 1 and comparative example 2 are solid at normal temperature, viscosity can not be tested, and the application at normal temperature can not be realized, and the application and construction can be realized only by heating. While examples 5-11 are all viscous liquids, which can be used at ambient temperature. The results show that the modified asphalt coating prepared by adopting the monohydroxy-terminated diblock copolymer as the modifier can not form effective physical crosslinking points due to the aggregation state structure, has lower cohesive strength and lower viscosity, can be applied at lower temperature and even normal temperature, and can overcome the problems of complex construction and smoke pollution existing in high-temperature construction of the coating.
In addition, after the coating is formed into a film and cured according to GB/T16777-2008 building waterproof coating experiment method, a coating with certain cohesive strength can be formed, because a polyisocyanate compound is introduced into the formula, and the hydroxyl-terminated diblock copolymer can react with the polyisocyanate compound to generate an isocyanate-terminated diblock copolymer in the preparation process. After construction, under the action of moisture in a base layer or air, the isocyanate-terminated diblock copolymer can undergo a crosslinking reaction, so that the paint has a certain mechanical strength, the standard requirement of JC/T852-1999 solvent-type rubber asphalt waterproof paint is met, and the final service performance of the paint can reach or even exceed the performance of the commercial SBS or SIS modified asphalt paint.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.