Polyurethane waterproof coating, preparation method and waterproof product

Abstract

The present application provides a polyurethane waterproof coating, a preparation method and a waterproof product. The polyurethane waterproof coating comprises raw materials in the following parts by weight: 206 parts of a polyurethane prepolymer, wherein the polyurethane prepolymer is formed by the reaction of hydroxyl-terminated polybutadiene acrylonitrile, organosilicon diol, polyether polyol and polyisocyanate; and based on 206 parts of the polyurethane prepolymer: 3 to 7 parts of an oxazolidine-terminated modified resin, 6 to 12 parts of a latent curing agent, 40 to 85 parts of an epoxy plasticizer, and 130 to 300 parts of an additive. In the polyurethane waterproof coating, the reaction of organosilicon diol, hydroxyl-terminated polybutadiene acrylonitrile and polyisocyanate can form an NCO-terminated prepolymer. The oxazolidine-terminated modified resin contains terminal oxazolidine, and the terminal oxazolidine hydrolyzes to release secondary hydroxyl and amino groups to participate in the reaction, so as to improve the peel strength of the waterproof material formed by the composite of the polyurethane coating and the coil.

Description

Technical Field

[0001] This application belongs to the field of waterproof coatings, and specifically relates to a polyurethane waterproof coating, a preparation method, and a waterproof product. Background Art

[0002] In recent years, the composite waterproofing process represented by coatings and rolls has become a major focus in the field of building / road and bridge waterproofing. The traditional construction restrictions on asphalt rolls are more stringent. Therefore, it is particularly important to adopt an environmentally friendly construction method to replace the open-flame baking process that produces toxic and harmful fumes.

[0003] The commonly used construction process for asphalt rolls is to use adhesives to lay the rolls. The construction method is to first apply the waterproof coating by scraping on the base surface, and then cover the asphalt waterproof roll on the coating layer. The coating layer also acts as a binder, perfectly bonding the base surface and the roll through a cold construction method. There are no harmful substance emissions during the construction process, achieving truly environmentally friendly construction. The combined use of the waterproof coating and the asphalt waterproof roll forms a virtual double-layer waterproofing, improving the waterproof stability. However, the peel strength of the waterproof material formed by the composite of traditional polyurethane waterproof coating and materials (such as asphalt rolls) is low, and the bonding effect is poor, affecting the application range of polyurethane waterproof coatings. Summary of the Invention

[0004] This application provides a polyurethane waterproof coating, a preparation method, and a waterproof product, aiming to improve the peel strength of the waterproof material formed by the composite of polyurethane waterproof coating and materials.

[0005] In the first aspect of this application, a polyurethane waterproof coating is provided, which includes the following raw materials in parts by weight:

[0006] Polyurethane prepolymer, 206 parts; the polyurethane prepolymer is formed by the reaction of hydroxyl-terminated polybutadiene acrylonitrile, organosilicon diol, polyether polyol, and polyisocyanate; and based on 206 parts of polyurethane prepolymer, oxazolidine-capped modified resin, 3 - 7 parts; latent curing agent, 6 - 12 parts; epoxy plasticizer, 40 - 85 parts; additive, 130 - 300 parts.

[0007] In a feasible implementation manner of the first aspect of this application, one molecule of the oxazolidine-capped modified resin further includes at least 2 epoxy groups.

[0008] In a feasible implementation manner of the first aspect of this application, the number-average molecular weight of the oxazolidine-capped modified resin is 1000 - 3000.

[0009] In a feasible implementation manner of the first aspect of this application, the epoxy equivalent of the oxazolidine-capped modified resin is 330 g / mol - 380 g / mol.

[0010] In a feasible embodiment of the first aspect of the present application, the oxazolidine-capped modified resin includes the following

[0011] Structure shown in Formula 1:

[0012]

[0013] In Formula 1, n is an integer from 1 to 2, X is an integer from 1 to 3, R is an alkyl group or a phenyl group, R1 is selected from H, an alkyl group or a phenyl group, and m is an integer from 1 to 5.

[0014] In a feasible embodiment of the first aspect of the present application, the number average molecular weight of the hydroxyl-terminated polybutadiene acrylonitrile is 2000 - 3500.

[0015] In a feasible embodiment of the first aspect of the present application, the hydroxyl value of the hydroxyl-terminated polybutadiene acrylonitrile is 0.50 - 0.70 mmol / g.

[0016] In a feasible embodiment of the first aspect of the present application, the polyurethane prepolymer is prepared from the following raw materials in parts by weight: 100 parts of hydroxyl-terminated polybutadiene acrylonitrile; and based on 100 parts of hydroxyl-terminated polybutadiene acrylonitrile: 14 - 35 parts of organosilicon diol; 30 - 50 parts of polyether polyol; 16 - 32 parts of polyisocyanate.

[0017] In a feasible embodiment of the first aspect of the present application, the number average molecular weight of the organosilicon diol is 1000 - 4000.

[0018] In a feasible embodiment of the first aspect of the present application, the organosilicon diol includes the structure shown in Formula 2 or

[0019] Structure shown in Formula 3:

[0020]

[0021] Among them, R1 and R2 are each independently an alkyl group, and n and m are each independently 8 - 50.

[0022] In a feasible embodiment of the first aspect of the present application, the epoxy plasticizer includes one or more of epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil, and epoxy sunflower oil.

[0023] In a feasible embodiment of the first aspect of the present application, the latent curing agent includes one or more of aldehyde imines, ketone imines, and oxazolidines.

[0024] In a feasible embodiment of the first aspect of the present application, the polyurethane waterproof coating satisfies at least one of the following characteristics:

[0025] a. The polyether polyol includes one or a combination of polyether diol and polyether triol;

[0026] b. The polyisocyanate includes one or a combination of aromatic diisocyanates and aliphatic diisocyanates; optionally one or several of toluene diisocyanate, diphenylmethane - 4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate;

[0027] c. The additive includes one or several of petroleum asphalt, pigments and fillers, and catalysts;

[0028] Optionally, the petroleum asphalt includes one or several of 50# asphalt, 70# asphalt, 90# asphalt, 110# asphalt, and 200# asphalt;

[0029] Optionally, the pigments and fillers include one or several of fumed silica, titanium dioxide, kaolin, heavy calcium carbonate, talc powder, barium sulfate, silica powder, nano calcium carbonate, calcium oxide, magnesium oxide, carbon black, and wollastonite;

[0030] Optionally, the catalysts include one or several of dibutyltin dilaurate, stannous octoate, lead isooctoate, bismuth isooctoate, and zinc neodecanoate.

[0031] The second aspect of the present application provides a preparation method of the polyurethane waterproof coating in the first aspect of the present application as described above, including the following steps:

[0032] React a predetermined weight portion of hydroxyl - terminated polybutadiene acrylonitrile, organosilicon diol, polyether polyol, polyisocyanate, epoxy plasticizer, and additive under the first condition to obtain a first reactant;

[0033] React the first reactant with an oxazolidine - terminated modified resin under the second condition to obtain a second reactant; react the second reactant with a latent curing agent under a catalytic condition to obtain the polyurethane waterproof coating.

[0034] In a feasible embodiment of the second aspect of the present application, in the step of reacting the first reactant with the oxazolidine - terminated modified resin under the second condition to obtain a second reactant, the preparation of the oxazolidine - terminated modified resin includes: reacting bisphenol A epoxy resin with glycidyl methacrylate or 3,4 - epoxyhexyl methacrylate through a free - radical polymerization reaction to obtain a reactant A; reacting the reactant A with a polyisocyanate to obtain a reactant B; reacting the reactant B with hydroxyoxazolidine to obtain the oxazolidine - terminated modified resin.

[0035] The third aspect of the present application provides a waterproof product, including: a waterproof coating and an asphalt waterproof roll covering the waterproof coating, wherein the waterproof coating is formed by the polyurethane coating provided in the first aspect of the present application as described above.

[0036] In the polyurethane waterproof coating of this application, a silicone diol with low surface energy and good system compatibility, a hydroxyl-terminated polybutadiene acrylonitrile, and a polyisocyanate react to form an NCO-terminated prepolymer. This prepolymer has good component compatibility with most materials (such as asphalt rolls), without segregation and swelling; further, the oxazolidine-terminated modified resin contains terminal oxazolidine. The terminal oxazolidine hydrolyzes to release secondary hydroxyl groups and amino groups. The secondary hydroxyl groups will undergo a cross-linking reaction with the NCO-terminated prepolymer, and the amino groups released by the hydrolysis of the amino groups and the latent curing agent can together undergo a ring-opening cross-linking reaction with the epoxy groups in the epoxy plasticizer, thereby better cross-linking the components in the polyurethane coating, especially the plasticizer. Since there is no free plasticizer in this system and no solvent is added, it avoids the migration and penetration of the plasticizer and the solvent into the asphalt roll and causing it to swell, and improves the peel strength of the waterproof material formed by the composite of the polyurethane coating and the asphalt roll. Specific Embodiments

[0037] In order to make the invention purpose, technical solution and beneficial technical effects of this application clearer, the following further details this application in combination with embodiments. It should be understood that the embodiments described in this specification are only for explaining this application and not for limiting this application.

[0038] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recorded; and any lower limit can be combined with other lower limits to form a range not explicitly recorded, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recorded. In addition, although not explicitly recorded, each point or single value between the range endpoints is included in this range. Thus, each point or single value can be used as its own lower limit or upper limit and combined with any other point or single value or combined with other lower limits or upper limits to form a range not explicitly recorded.

[0039] In the description herein, when a composition is described as containing, comprising or including a specific component, or when a process is described as containing, comprising or including a specific process step, it is contemplated that the composition of this application also consists essentially of or consists of the said components, and the process of this application also consists essentially of or consists of the said process steps.

[0040] Unless otherwise explicitly stated, the use of the terms "including", "comprising", "containing", "having" should generally be interpreted as open-ended and non-restrictive.

[0041] In the description herein, it should be noted that unless otherwise specified, "above" and "below" include this number, and "multiple" in "one or more" means more than two.

[0042] The above - mentioned invention content of this application does not intend to describe every disclosed embodiment or every implementation mode in this application. The following description more specifically illustrates exemplary embodiments. Throughout the application, guidance is provided through a series of embodiments, which can be used in various combinations. In each instance, the enumeration is only a representative group and should not be construed as exhaustive.

[0043] In order to improve the problem of low peel strength of asphalt waterproofing membranes, through a large number of experimental explorations, the inventor summarized and analyzed that the reason might be that the asphalt waterproofing membrane underwent a swelling effect, the intermolecular forces within the membrane decreased, resulting in a decrease in the cohesive force of the material and low peel strength. Further, the inventor delved deeper and believed that the reason for the swelling of the asphalt waterproofing membrane might be that the organic solvents, plasticizers, and other components contained in ordinary polyurethane waterproof coatings gradually migrated and penetrated into the asphalt in the membrane during use, causing a swelling effect on components such as asphalt, resulting in low peel strength of the asphalt waterproofing membrane.

[0044] In view of this, through a large number of experimental studies and demonstrations, the inventor provided a polyurethane waterproof coating, a preparation method, and a waterproof product in this application. In the first aspect of this application, the polyurethane waterproof coating is provided, which includes the following raw materials in parts by weight:

[0045] Polyurethane prepolymer, 206 parts; the polyurethane prepolymer is formed by reacting hydroxy - terminated polybutadiene acrylonitrile, organosilicon diol, polyether polyol, and polyisocyanate; and based on 206 parts of the polyurethane prepolymer: oxazolidine - terminated modified resin, 3 - 7 parts; latent curing agent, 6 - 12 parts; epoxy plasticizer, 40 - 85 parts; additive, 130 - 300 parts.

[0046] In the polyurethane waterproof coating provided in this application, the organosilicon diol with low surface energy and good system compatibility, hydroxy - terminated polybutadiene acrylonitrile react with polyisocyanate to form an NCO - terminated prepolymer. This prepolymer has good component compatibility with most materials (such as rolled asphalt), does not segregate and does not swell; further, the oxazolidine - terminated modified resin contains terminal oxazolidine. The terminal oxazolidine hydrolyzes to release secondary hydroxyl and amino groups. Its secondary hydroxyl groups will undergo a cross - linking reaction with the NCO - terminated prepolymer, and its amino groups and the amino groups released by the hydrolysis of the latent curing agent can together undergo a ring - opening cross - linking reaction with the epoxy groups in the epoxy plasticizer, thereby better cross - linking each component in the polyurethane coating, especially the plasticizer. Since there is no free plasticizer and no solvent added in this system, it avoids the migration and penetration of the plasticizer and solvent into the asphalt roll, preventing it from swelling, and improving the peel strength of the waterproof material formed by the composite of the polyurethane coating and the asphalt roll.

[0047] Meanwhile, the comprehensive introduction of the oxazolidine-capped modified resin, organosilicon diol, and hydroxy-terminated polybutadiene acrylonitrile in the coating of the present application can also improve the curing speed, adhesion, water resistance, tensile strength, tear strength, and flexibility of the polyurethane coating film. Moreover, the coating of the present application does not generate bubbles during the curing process and is less affected by the construction temperature and humidity.

[0048] In order to better reduce the migration and penetration of components in the coating into the coil interior, the effect of the oxazolidine-capped modified resin containing multiple epoxy groups is better. On the one hand, the oxazolidine-capped modified resin not only has the secondary hydroxyl and amino groups hydrolyzed from the terminal oxazolidine to crosslink with other components, but also the epoxy groups in its multiple epoxy groups and the epoxy plasticizer can undergo ring-opening crosslinking reactions with the amino groups of the latent curing agent, and can also react with the amino groups hydrolyzed from its own terminal oxazolidine. It can be seen that the crosslinking degree between the components is higher and the crosslinking density is greater, which can better reduce the migration of components in the polyurethane waterproof coating. Moreover, the introduction of multiple epoxy groups in the oxazolidine-capped modified resin can make the system cure faster, further improving the construction efficiency. In some embodiments, one molecule of the oxazolidine-capped modified resin also includes at least 2 epoxy groups. For example, it can be 2, 3, 4, 5, 6, or any value within the range of 2 to 6.

[0049] The inventors found that not only the functional groups in the oxazolidine-capped modified resin, but also the range of its number average molecular weight can affect the performance of the coating. Based on the terminal oxazolidine and multiple epoxy groups contained in the oxazolidine-capped modified resin, if its number average molecular weight is too small, it will have a certain impact on the crosslinking degree or bonding performance, and it is easy to cause unsatisfactory bonding performance. If its number average molecular weight is too large, the activity will be lower, which will also affect the crosslinking reaction between the components and thus affect the physical properties of the coating. In some embodiments, the number average molecular weight of the oxazolidine-capped modified resin is 1000 to 3000. For example, it can be 1000, 1500, 2000, 2500, 3000, or any value within the range of 1000 to 3000.

[0050] In some embodiments, the epoxy equivalent of the oxazolidine-capped modified resin is 330 g / mol to 380 g / mol. Further, the oxazolidine-capped modified resin of the present application also has a suitable range of epoxy equivalent, high activity, fast crosslinking speed, and high crosslinking density.

[0051] Bisphenol A epoxy resin contains multiple epoxy groups and has good activity. Using bisphenol A epoxy resin as the backbone structure, and then introducing glycidyl acrylate linkages, isocyanate linkages, and terminal oxazolidine can further improve the strength of the coating, such as bonding strength, tensile strength, and tear strength. In some embodiments, the oxazolidine-capped modified resin includes the structure of Formula 1 as follows:

[0052]

[0053] In Formula 1, n is an integer from 1 to 2, X is an integer from 1 to 3, R is an alkyl group or a phenyl group, each occurrence of R1 can be independently selected from H, an alkyl group or a phenyl group, and m is an integer from 1 to 5. For example, n can be 1 or 2, X can be 1, 2 or 3, and m can be 1, 2, 3, 4 or 5.

[0054] The plasticizer selected in this application is a plasticizer with an epoxy group. Exactly because it contains an epoxy group, it can undergo a ring-opening crosslinking reaction with the amino groups hydrolyzed from the oxazolidine-capped modified resin and the amino groups released by the hydrolysis of the latent curing agent, so that the plasticizer can be fixed in the coating film and become a part of the coating film itself, preventing it from migrating and penetrating into the coil material. In some embodiments, the epoxy plasticizer may include one or more of epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil, and epoxy sunflower oil.

[0055] The curing agent selected in this application is a latent curing agent that can hydrolyze and release amino groups. As can be seen from the above, the amino groups hydrolyzed from the curing agent in this application can undergo crosslinking reactions with various components in the coating, so that there are no free plasticizers and solvents in the coating system to reduce the swelling effect on the coil material. In some embodiments, the latent curing agent may include one or more of aldehyde imines, ketone imines, and oxazolidines.

[0056] In some embodiments, the polyurethane prepolymer is prepared from the following raw materials in parts by weight: hydroxyl-terminated polybutadiene acrylonitrile, 100 parts; and based on 100 parts of hydroxyl-terminated polybutadiene acrylonitrile: organosilicon diol, 14 - 35 parts; polyether polyol, 30 - 50 parts; polyisocyanate, 16 - 32 parts.

[0057] In this application, the polyurethane waterproof coating selects organosilicon diol with low surface energy and good system compatibility. The reaction of hydroxyl-terminated polybutadiene acrylonitrile with polyisocyanate can form an NCO-terminated prepolymer. The NCO-terminated prepolymer contains nitrile groups and acrylic groups introduced by hydroxyl-terminated polybutadiene acrylonitrile, etc., which can further improve the adhesion ability of the polyurethane film-forming resin. In some embodiments, the number average molecular weight of hydroxyl-terminated polybutadiene acrylonitrile can be 2000 - 3500. Optionally, its hydroxyl value is 0.50 mmol / g - 0.70 mmol / g.

[0058] Moreover, the NCO-terminated prepolymer in the present application further includes a polysiloxane molecular chain composed of a silicon-oxygen bond (-Si-O-Si-) introduced by organosilicon diol, which has a low surface energy and good compatibility with each component. Resins with terminal hydroxyl groups such as hydroxyl-terminated polybutadiene acrylonitrile, organosilicon diol, and polyether polyol react with isocyanate to form an NCO-terminated prepolymer. Then, the NCO-terminated prepolymer reacts with the secondary hydroxyl groups, amino groups hydrolyzed from the oxazolidine-terminated modified resin, and amino groups released by the latent curing agent, increasing the crosslinking degree of each component in the system.

[0059] In the present application, the introduction of the oxazolidine-terminated modified resin, organosilicon diol, and hydroxyl-terminated polybutadiene acrylonitrile comprehensively improves the adhesion, water resistance, heat resistance, weather resistance, and flexibility of the coating film. In some embodiments, the number-average molecular weight of the organosilicon diol can be 1000 - 4000, and the optional organosilicon diol can include the structures shown in Formula 2 or Formula 3 below:

[0060]

[0061] Among them, R1 and R2 can each independently be an alkyl group, and n and m can each independently be 8 - 50.

[0062] The present application can also select the following different types of polyether polyols, polyisocyanates, and additives for compounding according to requirements to obtain polyurethane coatings with different components. In some embodiments, the polyurethane waterproof coating can at least meet one of the following conditions: a. The polyether polyol includes one or a combination of polyether diol and polyether triol; b. The polyisocyanate includes one or a combination of aromatic diisocyanate and aliphatic diisocyanate; c. The additive includes one or several of petroleum asphalt, pigments and fillers, and catalysts.

[0063] The polyisocyanate can include one or several of toluene diisocyanate, diphenylmethane - 4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylxylylene diisocyanate.

[0064] The petroleum asphalt can include one or several of 50# asphalt, 70# asphalt, 90# asphalt, 110# asphalt, and 200# asphalt. The pigments and fillers can include one or several of fumed silica, titanium dioxide, kaolin, heavy calcium carbonate, talc powder, barium sulfate, silica powder, nano calcium carbonate, calcium oxide, magnesium oxide, carbon black, and wollastonite. The catalysts can include one or several of dibutyltin dilaurate, stannous octoate, lead isooctoate, bismuth isooctoate, and zinc neodecanoate.

[0065] The polyurethane waterproof coating provided by the present application can be prepared by the following method. The second aspect of the present application provides the preparation method, including:

[0066] Reacting a predetermined weight portion of hydroxyl-terminated polybutadiene acrylonitrile, silicone diol, polyether polyol, polyisocyanate, plasticizer and additive under a first condition to obtain a first reactant;

[0067] Reacting the first reactant with an oxazolidine-terminated modified resin under a second condition to obtain a second reactant; reacting the second reactant with a latent curing agent under a catalytic condition to obtain a polyurethane waterproof coating.

[0068] Specifically, the preparation of the first reactant may include mixing a predetermined weight portion of hydroxyl-terminated polybutadiene acrylonitrile, silicone diol, polyether triol, plasticizer, petroleum asphalt, pigment and filler uniformly in a high-speed disperser, and then transferring them to a synthesis kettle, stirring and heating to 100 °C to 110 °C, and dehydrating for 2 h to 3 h under a vacuum condition of -0.08 MPa to -0.1 MPa; cooling to 70 °C to 80 °C, adding diisocyanate under stirring, and then heating to 75 °C to 85 °C and reacting for 3 h to 4 h to obtain the first reactant.

[0069] Specifically, the preparation of the second reactant may include cooling the first reactant to 70 °C to 80 °C, adding an oxazolidine-terminated modified resin under stirring, and reacting for 1 h to 2 h to obtain the second reactant.

[0070] Specifically, the preparation of the polyurethane waterproof coating further includes cooling the second reactant to 50 °C to 60 °C, adding a latent curing agent and a catalyst under stirring, and reacting for 0.5 h to 1 h; cooling to below 50 °C, protecting with nitrogen, and discharging to obtain a one-component polyurethane waterproof coating.

[0071] The oxazolidine-terminated modified resin can be obtained by including free radical polymerization of bisphenol A epoxy resin and glycidyl methacrylate, and then further reacting with diisocyanate and hydroxyoxazolidine respectively.

[0072] In some embodiments, in the step of reacting the first reactant with the oxazolidine-terminated modified resin under a second condition to obtain a second reactant, the preparation of the oxazolidine-terminated modified resin includes: reacting bisphenol A epoxy resin with glycidyl methacrylate or 3,4-epoxyhexyl methacrylate by free radical polymerization to obtain a reactant A; reacting the reactant A with polyisocyanate to obtain a reactant B; reacting the reactant B with hydroxyoxazolidine to obtain the oxazolidine-terminated modified resin.

[0073] Specifically, the oxazolidine-terminated modified resin can be prepared by the following method:

[0074] S01: Put the dried bisphenol A epoxy resin E44 with a calculated amount into a reactor, add a mixed solvent of n-butanol and ethylene glycol monobutyl ether (mass ratio 1:2), start stirring until the epoxy resin is completely dissolved, and control the material temperature at 85°C; then dropwise add the calculated amount of glycidyl methacrylate (or 3,4-epoxyhexyl methacrylate) and benzoyl peroxide into the reactor, control a certain dropping reaction rate, continue to heat up and stir the reaction, control the temperature at 90°C - 95°C, keep the temperature constant for 6h - 7h, then evacuate and carry out vacuum distillation for 0.5h - 1h to obtain reactant A.

[0075] Among them, the amount of the mixed solvent of n-butanol and ethylene glycol monobutyl ether is 10% to 15% of the total mass of the reaction, and benzoyl peroxide is 0.3% to 0.5% of the total mass of the reaction. Reactant A may include the structure shown in Formula 4 below.

[0076]

[0077] In Formula 4, n is an integer from 1 to 2, and X is an integer from 1 to 3.

[0078] S02: Put the product reactant A obtained in step S01 into the reactor according to the calculated amount, add a mixed solvent of DMF and acetone (mass ratio 1:1), start stirring, and then add the calculated amount of diisocyanate and catalyst DABCO (1,4-diazabicyclo[2,2,2]octane) into the reactor. The mixed solvent of DMF and acetone (mass ratio 1:1) accounts for 12% - 25% of the total mass of the total preparation raw materials, and the catalyst DABCO (1,4-diazabicyclo[2,2,2]octane) accounts for one ten-thousandth to three ten-thousandths of the total mass of the total preparation raw materials. Heat up and stir the reaction in an oil bath, control the temperature at 75°C - 85°C, keep the temperature constant for 3h - 5h to obtain reactant B; reactant B may include the structure shown in Formula 5 below:

[0079]

[0080] In Formula 5, n is an integer from 1 to 2, X is an integer from 1 to 3; R is an alkyl group or a phenyl group.

[0081] S03: Control the temperature at 75°C - 85°C, continue to dropwise add the calculated amount of hydroxyoxazolidine into the reactor, keep the temperature constant for 2h - 3h under nitrogen protection, then evacuate, distill for 0.5h - 1h, cool down to 50°C - 60°C, and discharge to obtain the oxazolidine-capped modified resin. The structural formula of the oxazolidine-capped modified resin can be as shown in Formula 1 above.

[0082] Among them, the molar ratio of bisphenol A epoxy resin E44: glycidyl methacrylate: diisocyanate: hydroxyoxazoline is 1:(1-3):(1-1.05):(1-1.05).

[0083] Among them, the hydroxyoxazoline can be an oxazoline compound including 1 active hydroxyl group, and can include the structure shown in Formula 6 below:

[0084]

[0085] In Formula 6, R1 is H, an alkyl group or a phenyl group, and m is an integer from 1 to 5.

[0086] The hydroxyoxazoline can also include one or more of 2-isopropyl-3-hydroxyethyl-1,3-oxazoline, 3-hydroxyethyl-1,3-oxazoline, and 2-phenyl-3-hydroxyethyl-1,3-oxazoline.

[0087] The third aspect of the present application provides a waterproof product, including: a waterproof coating and an asphalt waterproof coiled material covered on the waterproof coating, wherein the waterproof coating is formed by the polyurethane coating provided in the first aspect of the present application above.

[0088] Embodiment

[0089] The following examples more specifically describe the content disclosed in the present application. These examples are only for illustrative purposes, because various modifications and changes within the scope of the content disclosed in the present application are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the instruments used in the examples are all commercially available.

[0090] The sources of the raw materials used in the following examples and comparative examples are as follows: hydroxyl-terminated polybutadiene acrylonitrile: number average molecular weight is 2000-3500, hydroxyl value is 0.50-0.70 mmol / g, purchased from Shandong Zibo Qilong Chemical Co., Ltd. Organosilicon diol, model SC-HP6002, purchased from Anhui Zhongen Chemical Co., Ltd. Polyether triol EP330N (functionality is 3, number average molecular weight is 5000), purchased from Shandong Bluestar Dongda Co., Ltd. Aldimine curing agent XY-401, purchased from Suzhou Xiangyuan New Materials Co., Ltd. Polyether diol DL-2000D (functionality is 2, number average molecular weight is 2000), purchased from Shandong Bluestar Dongda Co., Ltd. Other raw materials not specifically mentioned are all ordinary commercially available products.

[0091] Preparation Example 1

[0092] The oxazolidine-terminated modified resin is prepared by the following method:

[0093] S01: Put the calculated amount of dried bisphenol A epoxy resin E44 into the reactor, add the mixed solvent of n-butanol and ethylene glycol monobutyl ether (mass ratio 1:2), start stirring until the epoxy resin is completely dissolved, and control the material temperature at 85 °C; then dropwise add the calculated amount of glycidyl methacrylate and benzoyl peroxide into the reactor, control a certain dropping reaction rate, continue to heat up and stir the reaction, control the temperature at 92 °C, keep the temperature constant for 6 h, and then evacuate and distill under reduced pressure for 1 h to obtain reactant A1.

[0094] S02: Put the product reactant A1 obtained in step S01 into the reactor according to the calculated amount, add the mixed solvent of DMF and acetone (mass ratio 1:1), start stirring, and then add the calculated amount of tolylene diisocyanate and catalyst DABCO (1,4-diazabicyclo[2,2,2]octane) into the reactor. Heat up and stir the reaction in an oil bath, control the temperature at 80 °C, keep the temperature constant for 5 h to obtain reactant B1;

[0095] S03: Control the temperature at 80 °C, continue to dropwise add the calculated amount of 3-hydroxyethyl-1,3-oxazolidine into the reactor, keep the temperature constant for 3 h under nitrogen protection, then evacuate and distill for 1 h, cool down to 50 °C, and discharge to obtain the oxazolidine-terminated modified resin (number average molecular weight is 2100, epoxy equivalent is 350 g / eq).

[0096] Among them, the molar ratio of bisphenol A epoxy resin E44: glycidyl methacrylate: diisocyanate: hydroxyoxazolidine is 1:2.02:1.02:1.02, and the structural general formula is as shown in formula 1 above.

[0097] Preparation Example 2

[0098] The oxazolidine-terminated modified resin is prepared by the following method:

[0099] S01: Put the calculated amount of dried bisphenol A epoxy resin E44 into the reactor, add the mixed solvent of n-butanol and ethylene glycol monobutyl ether (mass ratio 1:2), start stirring until the epoxy resin is completely dissolved, and control the material temperature at 85 °C; then dropwise add the calculated amount of glycidyl methacrylate and benzoyl peroxide into the reactor, control a certain dropping reaction rate, continue to heat up and stir the reaction, control the temperature at 92 °C, keep the temperature constant for 6 h, and then evacuate and distill under reduced pressure for 1 h to obtain reactant A2.

[0100] S02: Put the product reactant A2 obtained in step S01 into the reactor in a calculated amount, add a calculated amount of a mixed solvent of DMF and acetone (mass ratio 1:1), start stirring, and then add a calculated amount of tolylene diisocyanate and the catalyst DABCO (1,4-diazabicyclo[2,2,2]octane) to the reactor. Heat and stir the reaction in an oil bath, control the temperature at 80 °C, and react at a constant temperature for 5 h to obtain reactant B2;

[0101] S03: Control the temperature at 80 °C, continue to drop a calculated amount of 3-hydroxyethyl-1,3-oxazolidine into the reactor, react at a constant temperature for 3 h under nitrogen protection, then evacuate, distill for 1 h, cool to 50 °C, and discharge to obtain the oxazolidine-capped modified resin (number average molecular weight is 3400, epoxy equivalent is 242 g / eq).

[0102] Among them, the molar ratio of bisphenol A type epoxy resin E44: glycidyl methacrylate: diisocyanate: hydroxyoxazolidine is 1:4.02:1.02:1.02.

[0103] Preparation Example 3

[0104] Compared with Preparation Example 1, the main difference is that the backbone resin of the oxazolidine-capped modified resin is other resins without bisphenol rigid structure, poly[(2-epoxyethyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether.

[0105] The oxazolidine-capped modified resin is prepared by the following method:

[0106] S01: Put a calculated amount of dried poly[(2-epoxyethyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether into the reactor, add a calculated amount of a mixed solvent of n-butanol and ethylene glycol monobutyl ether (mass ratio 1:2), start stirring until the resin is completely dissolved, and control the material temperature at 85 °C; then drop a calculated amount of glycidyl methacrylate and benzoyl peroxide into the reactor, control a certain dropping reaction rate, continue to heat and stir the reaction, control the temperature at 92 °C, react at a constant temperature for 6 h, then evacuate and distill under reduced pressure for 1 h to obtain reactant A3.

[0107] S02: Weigh the product reactant A3 obtained in step S01 and put it into the reactor in a calculated amount, add a calculated amount of a mixed solvent of DMF and acetone (mass ratio 1:1), start stirring, and then add a calculated amount of tolylene diisocyanate and the catalyst DABCO (1,4-diazabicyclo[2,2,2]octane) to the reactor. Heat and stir the reaction in an oil bath, control the temperature at 80 °C, and react at a constant temperature for 5 h to obtain reactant B3;

[0108] S03: Control the temperature at 80 °C, continue to drop the calculated amount of 3 - hydroxyethyl - 1,3 - oxazolidine into the reactor, keep the temperature constant under nitrogen protection for 3 h, then evacuate to vacuum and distill for 1 h, cool down to 50 °C, and discharge to obtain the oxazolidine - terminated modified resin (number - average molecular weight is 1960, epoxy equivalent is 326 g / eq).

[0109] Among them, the molar ratio of poly[(2 - epoxyethyl)-1,2 - cyclohexanediol] 2 - ethyl - 2 - (hydroxymethyl)-1,3 - propanediol ether: glycidyl methacrylate: diisocyanate: hydroxyoxazolidine is 1:2.02:1.02:1.02.

[0110] Example 1

[0111] The one - component polyurethane waterproof coating for bonding asphalt shingles in this example includes the following components in parts by weight:

[0112] Hydroxyl - terminated polybutadiene acrylonitrile, 100 parts by weight; organosilicon diol, 32 parts by weight; polyether triol, 48 parts by weight; epoxy - modified linseed oil, 74 parts by weight; 50# asphalt, 14 parts by weight; toluene diisocyanate, 28 parts by weight; talcum powder, 100 parts by weight; heavy calcium carbonate, 160 parts by weight; oxazolidine - terminated modified resin (the above - prepared Example 1, number - average molecular weight is 2100 - 2400, epoxy equivalent is 350 g / eq), 6 parts by weight; aldehyde imine curing agent XY - 401, 11 parts by weight; stannous octoate, 0.4 parts by weight.

[0113] The preparation method of the one - component polyurethane waterproof coating in this example includes the following steps:

[0114] (1) Mix the predetermined parts by weight of hydroxyl - terminated polybutadiene acrylonitrile, organosilicon diol, polyether triol, epoxy - modified linseed oil, 50# asphalt, and pigments and fillers evenly in a high - speed disperser, then transfer to a synthesis kettle, stir and heat up to 105 °C, dehydrate under a vacuum condition of - 0.09 MPa for 2.5 h; then cool down to 75 °C, add diisocyanate under stirring, and then heat up to 80 °C and react for 3.5 h to obtain the first reactant;

[0115] (2) Cool the first reactant to 75 °C, add the oxazolidine - terminated modified resin under stirring, and react for 1.5 h to obtain the second reactant;

[0116] (3) Cool the second reactant to 55 °C, add aldehyde imine and catalyst under stirring, react for 0.8 h, then cool down to below 50 °C, protect with nitrogen, and discharge to obtain the polyurethane waterproof coating.

[0117] Example 2

[0118] The one-component polyurethane waterproof coating for bonding asphalt coils in this embodiment comprises the following components in parts by weight: hydroxyl-terminated polybutadiene acrylonitrile, 100 parts by weight; organosilicon diol, 30 parts by weight; polyether triol, 50 parts by weight; epoxy linseed oil, 74 parts by weight; 50# asphalt, 14 parts by weight; toluene diisocyanate, 27 parts by weight; talcum powder, 100 parts by weight; heavy calcium carbonate, 160 parts by weight; oxazolidine-capped modified resin (the same as in Example 1), 6 parts by weight; aldehyde imine curing agent XY-401, 11 parts by weight; stannous octoate, 0.4 part by weight.

[0119] The preparation process of the one-component polyurethane waterproof coating in this embodiment is basically the same as that in Example 1 and will not be elaborated here.

[0120] Example 3

[0121] The one-component polyurethane waterproof coating for bonding asphalt coils in this embodiment comprises the following components in parts by weight: hydroxyl-terminated polybutadiene acrylonitrile, 100 parts by weight; organosilicon diol, 30 parts by weight; polyether triol, 48 parts by weight; epoxy linseed oil, 74 parts by weight; 50# asphalt, 15 parts by weight; toluene diisocyanate, 28 parts by weight; talcum powder, 100 parts by weight; heavy calcium carbonate, 160 parts by weight; oxazolidine-capped modified resin (the same as in Example 1), 7 parts by weight; aldehyde imine curing agent XY-401, 11 parts by weight; stannous octoate, 0.4 part by weight.

[0122] The preparation process of the polyurethane waterproof coating in this embodiment is basically the same as that in Example 1 and will not be elaborated here.

[0123] Example 4

[0124] The one-component polyurethane waterproof coating for bonding asphalt coils in this embodiment comprises the following components in parts by weight: hydroxyl-terminated polybutadiene acrylonitrile, 90 parts by weight; organosilicon diol, 35 parts by weight; polyether triol, 48 parts by weight; epoxy linseed oil, 76 parts by weight; 50# asphalt, 14 parts by weight; toluene diisocyanate, 28 parts by weight; talcum powder, 100 parts by weight; heavy calcium carbonate, 160 parts by weight; oxazolidine-capped modified resin (the same as in Example 1), 6 parts by weight; aldehyde imine curing agent XY-401, 11 parts by weight; stannous octoate, 0.4 part by weight.

[0125] The preparation process of the polyurethane waterproof coating in this embodiment is basically the same as that in Example 1 and will not be elaborated here.

[0126] Example 5

[0127] Compared with Example 1, the difference is that the oxazolidine-capped modified resin used is the above Preparation Example 2, with a number average molecular weight of 3300 - 3600 and an epoxy equivalent of 242 g / eq.

[0128] The preparation process of the polyurethane waterproof coating in this example is basically the same as that in Example 1, and will not be elaborated here.

[0129] Example 6

[0130] Compared with Example 1, the difference is that the oxazolidine-terminated modified resin used is the above Preparation Example 3, the number-average molecular weight of the obtained oxazolidine-terminated modified resin is 1960, and the epoxy equivalent is 326 g / eq; and the backbone resin of the oxazolidine-terminated modified resin is poly[(2-oxiranylmethyl)-1,2-cyclohexanediol] 2-ethyl-2-(hydroxymethyl)-1,3-propanediol ether without bisphenol rigid structure.

[0131] The preparation process of the polyurethane waterproof coating in this example is basically the same as that in Example 1, and will not be elaborated here.

[0132] Comparative Example 1

[0133] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those in Example 1. The difference is that the hydroxyl-terminated polybutadiene acrylonitrile in Example 1 is removed and replaced with polyether diol DL-2000D of the same weight part. The functionality is 2, the number-average molecular weight is 2000, and it is purchased from Shandong Bluestar Dongda Co., Ltd.

[0134] The preparation processes of the polyurethane waterproof coatings in each comparative example are roughly the same as those in Example 1, and will not be elaborated here.

[0135] Comparative Example 2

[0136] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those in Example 1. The difference is that the silicone diol in Example 1 is removed and replaced with polyether diol DL-2000D of the same weight part. The functionality is 2, the number-average molecular weight is 2000, and it is purchased from Shandong Bluestar Dongda Co., Ltd.

[0137] Comparative Example 3

[0138] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those in Example 1. The difference is that the hydroxyl-terminated polybutadiene acrylonitrile and silicone diol in Example 1 are removed and replaced with polyether diol DL-2000D of the same weight part. The functionality is 2, the number-average molecular weight is 2000, and it is purchased from Shandong Bluestar Dongda Co., Ltd.

[0139] Comparative Example 4

[0140] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those of Example 1, except that the oxazolidine-terminated modified resin in Example 1 is removed and replaced by an equal weight portion of aldimine XY-401 (purchased from Suzhou Xiangyuan New Materials Co., Ltd.), and the plasticizer is replaced by an equal weight portion of 52# chlorinated paraffin (purchased from Jiangxi Oriental Julong Chemical Co., Ltd.).

[0141] Comparative Example 5

[0142] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those of Example 1, except that the oxazolidine end-capped modified resin in Example 1 is removed and replaced by an equal weight portion of bisphenol A type epoxy resin E44 (purchased from Baling Petrochemical Company).

[0143] Comparative Example 6

[0144] A one-component polyurethane waterproof coating, whose composition and preparation process are similar to those of Example 1, except that it does not contain plasticizer epoxy linseed oil.

[0145] Performance Testing

[0146] The performance of the one-component polyurethane waterproof coating for bonding asphalt coils prepared in each embodiment and comparative example was tested, and the test performance is shown in Table 1.

[0147] (1) Except for the peel strength test, the other performance test methods in Table 1 are carried out in accordance with JC / T2435-2018.

[0148] (2) The test method of the composite peel strength of the roll material is as follows: the prepared coating layer is overlapped with the asphalt waterproofing roll material, and the 180° peel strength is tested after the overlap. Specifically, the polyurethane waterproofing coating is applied to the base surface by cold construction, and the coating thickness is 1.5±0.2mm. After the coating is completed, the asphalt waterproofing roll material is laid on the coating layer during the coating adaptation period, and the roll material is rolled tightly so that the roll material and the coating are in a fully adhered state. After curing for 168 hours, the 180° peel strength is tested. The specific test steps are as follows:

[0149] The size and preparation method of the test piece: 1. Cut the asphalt waterproofing membrane and keep its bonding surface size at the preset size, which is 70*50mm; 2. Apply the polyurethane waterproof coating to the base surface; 3. Then directly lay the cut asphalt membrane on the polyurethane waterproof coating and compact it to make it fully adhered; 4. Cure the prepared test piece under standard curing conditions for 168 hours.

[0150] Test method: Mount the cement mortar surface of the above test piece on the fixture at one end of the electronic tensile testing machine, and bend the unbonded surface of the coil in the above test piece opposite to the bonding surface by 180° and clamp it in the fixture at the other end of the testing machine. Pay attention to accurately positioning the test piece between the chucks to ensure that the applied tensile force is evenly distributed across the width of the test piece. Start the testing equipment and set the tensile speed to 100 mm / min.

[0151]

[0152] From the data in the table, it can also be seen from the comparison between Examples 1-4 and Comparative Examples 1-4 that in terms of various properties such as the bonding performance of the coating, the composite peel strength with the coil, and the peel failure mode in Examples 1-4 are more excellent; the bonding performance of the coating and the composite peel strength with the coil in Comparative Examples 1-4 are significantly lower than those in Examples 1-4. From the data of the composite peel strength (N / mm) with the asphalt coil and the failure mode, it can be clearly seen that the introduction of reactant C improves the composite peel strength with the asphalt coil, and the combined use of hydroxyl-terminated acrylonitrile-butadiene rubber and silicone diol can play a certain synergistic effect to jointly improve the bonding effect on the waterproof coil. In Example 5, the molecular weight of the oxazolidine-terminated modified resin is too large, which affects the reaction activity of the modified resin, the crosslinking density of the system decreases, the drying time is longer, and the strength decreases, such as the tensile strength, tear strength, and bonding strength; in Example 6, the backbone resin of the oxazolidine-terminated modified resin used is an alicyclic epoxy resin without a bisphenol rigid structure, and it can be clearly seen that the reaction activity also decreases, and the strength also decreases, such as the tensile strength, tear strength, and bonding strength, but it has little effect on the composite peel strength with the asphalt coil; in Comparative Example 5, since the resin without an oxazolidine end group is used, the properties such as peel strength and bonding strength decrease; in Comparative Example 6, since epoxy linseed oil plasticizer is not contained, the tensile strength / bonding strength is significantly increased, but the elongation at break decreases significantly, and the composite peel strength with the asphalt coil also decreases significantly. This may be due to the lack of the toughening effect of the epoxy plasticizer, and the coating layer is significantly rigid. Due to the difference in interfacial stress between this rigid layer and the flexible coil layer, the peel strength decreases.

[0153] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A polyurethane waterproof coating, characterized in that: The polyurethane waterproof coating comprises the following raw materials in parts by weight: Polyurethane prepolymer, 206 parts; the polyurethane prepolymer is formed by reacting hydroxy-terminated polybutadiene acrylonitrile, silicone diol, polyether polyol and polyisocyanate; and all based on 206 parts of polyurethane prepolymer: Oxazolidine end-capped modified resin, 3 to 7 parts; Latent curing agent, 6 to 12 parts; Epoxy plasticizer, 40-85 parts; Additives, 130-300 parts; The oxazolidine-terminated modified resin comprises a structure as shown in Formula 1: In Formula 1, n is an integer of 1 to 2, X is an integer of 1 to 3, R is an alkyl group or a phenyl group, R1 is selected from H, an alkyl group or a phenyl group, and m is an integer of 1 to 5.

2. The polyurethane waterproof coating according to claim 1, characterized in that: The number average molecular weight of the oxazolidine-terminated modified resin is 1000-3000.

3. The polyurethane waterproof coating according to claim 1, characterized in that: The epoxy equivalent of the oxazolidine-terminated modified resin is 330 g / mol to 380 g / mol.

4. The polyurethane waterproof coating according to claim 1, characterized in that: The number average molecular weight of the hydroxy-terminated polybutadiene acrylonitrile is 2000-3500.

5. The polyurethane waterproof coating according to claim 1, characterized in that: The hydroxyl value of the hydroxy-terminated polybutadiene acrylonitrile is 0.50 mmol / g to 0.70 mmol / g.

6. The polyurethane waterproof coating according to claim 1, characterized in that: The polyurethane prepolymer comprises the following raw materials in parts by weight: 100 parts of terminal hydroxyl polybutadiene acrylonitrile; and based on 100 parts of terminal hydroxyl polybutadiene acrylonitrile: 14-35 parts of organosilicon diol; 30-50 parts of polyether polyol; and 16-32 parts of polyisocyanate.

7. The polyurethane waterproof coating according to claim 1, characterized in that: The number average molecular weight of the organosilicon diol is 1000-4000.

8. The polyurethane waterproof coating according to claim 1, characterized in that: The organosilicon diol comprises a structure as shown in Formula 2 or Formula 3: Wherein, R1 and R2 are each independently an alkyl group, and n and m are each independently 8 to 50.

9. The polyurethane waterproof coating according to claim 1, characterized in that: The epoxy plasticizer includes one or more of epoxy soybean oil, epoxy linseed oil, epoxy cottonseed oil, epoxy rice bran oil and epoxy sunflower oil.

10. The polyurethane waterproof coating according to claim 1, characterized in that: The latent curing agent includes one or more of aldimines, ketimines and oxazolidines.

11. The polyurethane waterproof coating according to claim 1, characterized in that: The polyurethane waterproof coating meets at least one of the following characteristics: a. The polyether polyol comprises one or a combination of a polyether diol and a polyether triol; b. The polyisocyanate comprises one or a combination of an aromatic diisocyanate and an aliphatic diisocyanate; c. The additives include one or more of petroleum asphalt, pigments, fillers and catalysts.

12. The polyurethane waterproof coating according to claim 11, characterized in that: The polyisocyanate includes one or more of toluene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate and tetramethyl-m-xylylene diisocyanate; The petroleum asphalt includes one or more of 50# asphalt, 70# asphalt, 90# asphalt, 110# asphalt and 200# asphalt; The pigments and fillers include one or more of fumed silica, titanium dioxide, kaolin, heavy calcium, talcum powder, barium sulfate, silicon micropowder, nano calcium carbonate, calcium oxide, magnesium oxide, carbon black and wollastonite; The catalyst comprises one or more of dibutyltin dilaurate, stannous octoate, lead isooctanoate, bismuth isooctanoate and zinc neodecanoate.

13. The method for preparing the polyurethane waterproof coating according to any one of claims 1 to 12, characterized in that: include: Allowing predetermined weight portions of hydroxy-terminated polybutadiene acrylonitrile, silicone diol, polyether polyol, polyisocyanate, epoxy plasticizer and additive to react under a first condition to obtain a first reactant; allowing the first reactant and the oxazolidine-terminated modified resin to react under a second condition to obtain a second reactant; The second reactant and the latent curing agent are reacted under catalytic conditions to obtain the polyurethane waterproof coating.

14. The method for preparing the polyurethane waterproof coating according to claim 13, characterized in that: In the step of reacting the first reactant and the oxazolidine-terminated modified resin under the second condition to obtain the second reactant, the preparation of the oxazolidine-terminated modified resin includes: Bisphenol A epoxy resin and glyceryl methacrylate or 3,4-epoxyhexyl methacrylate are subjected to free radical polymerization reaction to obtain reactant A; reactant A is reacted with polyisocyanate to obtain reactant B; reactant B is reacted with hydroxy oxazolidine to obtain the oxazolidine-terminated modified resin.

15. A waterproof product comprising: A waterproof coating and an asphalt waterproof coiled material covering the waterproof coating, wherein the waterproof coating is formed by the polyurethane waterproof coating according to any one of claims 1 to 12.

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