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 degradation, performance loss and other adverse effects, 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 the use of the modified asphalt paint described above.
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 single epoxy-terminated diblock copolymer, and the single epoxy-terminated diblock copolymer has the structural formula:wherein R is1 Is C1 -C10 A is a monoalkenyl arene polymer segment, C is a butadiene and/or isoprene polymer segment, R2 Is C1 -C12 The modified asphalt coating also includes a ketimine latent curing agent.
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.
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 -C8 Alkyl ethers of (a). Preferably, said R2 Selected from the group consisting of 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, the R2 Selected from methyl ethyl ether, methyl isopropyl ether, diethyl ether, ethyl isopropyl ether.
According to some embodiments of the invention, the monoepoxy-terminated diblock copolymer is a monoepoxy-terminated styrene-butadiene/isoprene diblock copolymer.
According to some embodiments of the invention, the a is present in the monoepoxy-terminated diblock copolymer in an amount of from 10 to 50% by mass, preferably from 20 to 40% by mass. More preferably 25 to 35%.
According to some embodiments of the invention, the single epoxy-terminated diblock copolymer has a number average molecular weight of 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 10:0.5-3:1.5-15: 0.05 to 0.5.
Further, the raw materials of the modified asphalt paint also comprise 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, 5-30 parts of a single 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. Preferably, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 8-20 parts of a single 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 parts of a curing accelerator.
Further, the asphalt is matrix 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 ketimine DA315 and ketimine DA360A.
Further, the plasticizer is one or a combination of more of aromatic oil, naphthenic oil and paraffinic oil.
Further, the curing accelerator is one or a combination of a plurality of aniline accelerators and fatty amine accelerators, for example, the curing accelerator is one or a combination of a plurality of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine and fatty amine.
According to some embodiments of the invention, the raw materials of the modified asphalt paint further comprise one or a combination of more of reactive diluents, fillers and coupling agents.
According to some specific embodiments of the invention, the raw materials of the modified asphalt paint comprise, by weight, 100 parts of asphalt, 5-30 parts of single epoxy end-capped diblock copolymer, 15-150 parts of plasticizer, 0.5-5.0 parts of ketimine latent curing agent, 0.1-2 parts of curing accelerator, 0-10 parts of reactive diluent, 0-120 parts of filler and 0-5 parts of coupling agent. Preferably, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 8-20 parts of a single epoxy end-capped 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 carbonate, light calcium carbonate, kaolin, attapulgite, bentonite and silicon micropowder.
Further, the reactive diluent is one or a combination of a plurality of single epoxy reactive diluents, double epoxy reactive diluents and multiple epoxy reactive diluents.
Further, the coupling agent is a silane coupling agent, such as one or more of gamma-aminopropyl triethoxysilane (KH 550), gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane (KH 570).
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 a Single epoxy 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 said diblock copolymer having an activated end with an alkylene oxide and an haloalkylene oxide in sequence to give a polymer having said activated endA structural monoepoxy-terminated diblock copolymer;
s2, preparing modified asphalt paint
And mixing all the raw materials of the modified asphalt coating to obtain the modified asphalt coating.
Further, the implementation of step S1 includes:
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;
step S13, alkylene oxide and alkyl halide are sequentially added into a solution system containing the diblock copolymer with the activated end, so that the diblock copolymer with the activated end sequentially reacts with the alkylene oxide and the alkyl halide to obtain the diblock copolymer with the monoepoxy end.
Further, the implementation of step S2 includes:
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 ℃, adding the single epoxy-terminated diblock copolymer, and dissolving the single 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 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 several of RLi, R is an alkane 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 ℃; in the step S12, the reaction is carried out at 40-60 ℃; in step S13, the reactions with alkylene oxide and haloalkylene oxide in this order are carried out at 40 to 60 ℃.
In some embodiments, the alkylene oxide is selected from the group consisting of one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 2-pentane oxide, hexane oxide, phenyl ethylene oxide.
In some embodiments, the epoxyhaloalkane is selected from the group consisting of one or more of epichlorohydrin, epoxybromopropane, 1, 2-epoxychlorobutane.
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 paint or the modified asphalt paint prepared by the preparation method of the modified asphalt paint.
Further, the waterproof material may further include a modified asphalt waterproof roll disposed on at least one surface of the coating layer.
Still further, 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 provided by the invention adopts the single epoxy end-capped 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 consumption is reduced, and the adverse consequences of degradation, coking, gel and the like of the polymer in the high-temperature process are effectively alleviated. 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 diblock copolymer with a single epoxy end cap as a modifier, and the ketimine latent curing agent is introduced into the formula, and can be subjected to crosslinking reaction with epoxy groups in the modifier under the action of moisture in a base layer or air after construction, so that a triblock copolymer similar to SBS or SIS is formed in situ, and the modified asphalt coating is endowed with certain cohesive strength and mechanical property, meets the application requirements of waterproof materials, and does not influence the service performance of end products.
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 single epoxy end-capped diblock copolymer is introduced into the modified asphalt paint as a modifier, and an effective physical crosslinking point cannot be formed by utilizing the aggregated structure of the single epoxy end-capped 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 aggregated structure of the single epoxy end-capped 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 ketimine latent curing agent is introduced into the formula, and can be subjected to crosslinking reaction with epoxy groups in the modifier under the action of moisture in a base layer or air after construction, so that a triblock copolymer similar to SBS or SIS is formed in situ, and the service performance of a terminal product is not affected.
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.
Part of the raw material sources in the following examples:
asphalt: 70# asphalt, china petrochemical Co., ltd.
Reactive diluent: 1, 6-hexanediol diglycidyl ether, guangzhou by new materials limited; alternatively, epoxidized soybean oil, shenzhen Kong chemical Co., ltd.
Ketimine latent curing agent: DA315 or DA360A, wittish chemical Co., ltd.
Curing accelerator: DMP30, guangzhou chemical industry Co., ltd; alternatively, dodecylamine, shandong Hao chemical Co., ltd.
Silane coupling agent: KH550 or KH570, national pharmaceutical chemicals limited.
And (3) a plasticizer: naphthenic oil.
Example 1
The single epoxy-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, 1.0ml of ethylene oxide was added and reacted for 15 minutes, and 1.2ml of epichlorohydrin was added and reacted for 15 minutes, followed by termination with 1.8ml of ethanol. 264 anti-aging agent with the mass percentage of 1.5 percent is added according to the mass measurement of the polymerization end 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 monoepoxy terminated styrene-butadiene segmented copolymer is obtained. GPC test number average molecular weight of monoepoxy terminated styrene-butadiene block copolymer was 56400 and molecular weight distribution was 1.08.
Example 2
The single epoxy-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, 0.5ml of propylene oxide was added and reacted for 15 minutes, and then 0.6ml of epichlorohydrin was added and reacted for 15 minutes, and the reaction was terminated with 0.9ml of ethanol. 264 anti-aging agent with the mass percentage of 1.5 percent is added according to the mass measurement of the polymerization end 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 monoepoxy terminated styrene-butadiene segmented copolymer is obtained. GPC measured that the number average molecular weight of the monoepoxy-terminated styrene-butadiene block copolymer was 142500 and the molecular weight distribution was 1.10.
Example 3
The single epoxy-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, 1.4ml of ethylene oxide was added and reacted for 15min, and then 1.6ml of epichlorohydrin was added and reacted for 15min, followed by termination with 2.4ml of ethanol. 264 anti-aging agent with the mass percentage of 1.5 percent is added according to the mass measurement of the polymerization end 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 monoepoxy-terminated styrene-isoprene segmented copolymer is obtained. GPC measurement showed that the number average molecular weight of the monoepoxy-terminated styrene-isoprene block copolymer was 43500, and the molecular weight distribution was 1.06.
Example 4
The single epoxy-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, 3.5ml of propylene oxide was added and reacted for 15min, and then 4.2ml of epichlorohydrin was added and reacted for 15min, followed by termination with 6.0ml of ethanol. 264 anti-aging agent with the mass percentage of 1.5 percent is added according to the mass measurement of the polymerization end 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 monoepoxy-terminated styrene-isoprene segmented copolymer is obtained. GPC measured that the number average molecular weight of the monoepoxy-terminated styrene-butadiene block copolymer was 18250 and the molecular weight distribution was 1.08.
Example 5
The modified asphalt paint provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of No. 70 asphalt, 14 parts of modifier (styrene-butadiene diblock copolymer prepared in example 1), 80 parts of plasticizer aromatic oil, 2 parts of ketimine latent curing agent DA315, 30 parts of curing accelerator DMP, 1 part of reactive diluent 1, 6-hexanediol diglycidyl ether, 40 parts of filler heavy calcium 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 of the relative vacuum degree of-0.09 MPa, and dehydrating for 3 hours to obtain a first mixture;
(2) Heating the first mixture to 140 ℃, adding the 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 uniformly mixing and stirring 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, 20 parts of modifier (styrene-butadiene diblock copolymer prepared in example 1), 100 parts of plasticizer aromatic oil, 4 parts of ketimine latent curing agent DA315, 30 parts of curing accelerator DMP, 2 parts of reactive diluent 1, 6-hexanediol diglycidyl ether, 50 parts of filler heavy calcium and 550 parts of coupling agent KH.
The preparation method is the same as in example 5.
Example 7
The modified asphalt paint 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, 1 part of ketimine latent curing agent DA315, 30 parts of curing accelerator DMP, 2 parts of reactive diluent 1, 6-hexanediol diglycidyl ether, 50 parts of filler heavy calcium and 550 parts of coupling agent KH.
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 3.5 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 2.0h.
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 1.0h.
Example 11
The modified asphalt paint provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 20 parts of modifier (styrene-isoprene diblock copolymer prepared in example 4), 100 parts of plasticizer naphthenic oil, 2 parts of ketimine latent curing agent DA315 and 30 parts of curing accelerator DMP.
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.
The modified asphalt coatings of examples 5 to 11 and comparative examples 1 to 2 were subjected to a test for viscosity at 25℃according to GB/T10247-2008 "viscosity test method", and a test for heat resistance, low-temperature flexibility, water impermeability and adhesive strength according to GB/T16777-2008 "building waterproof coating test method" and JC/T852-1999 "solvent type rubber asphalt waterproof coating", and the results are shown in Table 1.
Table 1 shows the results of performance tests of the modified asphalt coatings 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 result shows that the modified asphalt coating prepared by adopting the diblock copolymer with the single epoxy end-capped 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 in construction at lower temperature 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 paint is formed into a film and cured according to GB/T16777-2008 'building waterproof paint experiment method', a coating with certain cohesive strength can be formed, because a ketimine latent curing agent is introduced into the formula, and after construction, the ketimine latent curing agent can be subjected to crosslinking reaction with epoxy groups in a modifier under the action of moisture in a base layer or air, so that the paint has 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.