CN115418162B

CN115418162B - Double-component polyurethane waterproof coating composition, preparation method thereof and structure using double-component polyurethane waterproof coating composition

Info

Publication number: CN115418162B
Application number: CN202211214151.8A
Authority: CN
Inventors: 何宏林; 陈立义; 陈开寿
Original assignee: Foshan Keshun Building Material Co ltd; Keshun Waterproof Technology Co Ltd
Current assignee: Foshan Keshun Building Material Co ltd; Keshun Waterproof Technology Co Ltd
Priority date: 2022-09-30
Filing date: 2022-09-30
Publication date: 2023-05-12
Anticipated expiration: 2042-09-30
Also published as: CN115418162A

Abstract

The application discloses a double-component polyurethane waterproof coating composition, a preparation method thereof and a structure using the double-component polyurethane waterproof coating composition. The two-component polyurethane waterproof coating composition comprises a component A and a component B, wherein the component A comprises isocyanate-terminated polyurethane, and the raw material components of the isocyanate-terminated polyurethane comprise polyether polyol, hydroxyl-terminated polybutadiene acrylonitrile and isocyanate, and the isocyanate is at least one of diisocyanate or polyisocyanate; the component B comprises a plasticizer, a curing agent, a pigment filler, a tackifier, a dispersing agent and a catalyst, wherein the contents of the plasticizer, the curing agent, the pigment filler, the tackifier, the dispersing agent and the catalyst are respectively defined as the content of the plasticizer, the curing agent, the pigment filler, the tackifier, the dispersing agent and the catalyst, and the catalyst is selected from a carbamate catalyst and/or an allophanate catalyst. The adhesive force of the isolating film of the two-component polyurethane waterproof coating and the asphalt waterproof coiled material can be improved.

Description

Double-component polyurethane waterproof coating composition, preparation method thereof and structure using double-component polyurethane waterproof coating composition

Technical Field

The application belongs to the technical field of waterproof coating, and in particular relates to a double-component polyurethane waterproof coating composition, a preparation method thereof and a structure applying the double-component polyurethane waterproof coating composition.

Background

In recent years, a composite waterproof process represented by paint and coiled materials becomes a big hot spot in the field of building/road bridge waterproof, wherein the most commonly used construction process is to firstly carry out priming construction on a base surface by waterproof paint, then attach an asphalt waterproof coiled material on a paint layer, and the paint layer acts as a second waterproof layer and also acts as an adhesive, so that the base surface and the asphalt waterproof coiled material are adhered together through a cold construction method, the composite use of the waterproof paint and the asphalt waterproof coiled material is realized, the actual double-channel waterproof is formed, and the waterproof stability is further improved.

The asphalt waterproof coiled material is generally composed of a protective film, an asphalt layer and a separation film, and when in construction, the separation film is generally removed firstly, and then the asphalt layer of the asphalt waterproof coiled material is attached to the coating layer. However, since the isolating film of the asphalt waterproof roll and the asphalt layer are already laminated into a whole, the isolating film is not easy to be torn off manually for cold construction. In addition, after the film is uncovered, the asphalt layer is directly contacted with the coating layer, and components of the asphalt layer and the coating layer can be migrated and separated out, so that the performances of the asphalt coiled material and the coating film are influenced or reduced, and the waterproof performance is reduced.

Disclosure of Invention

The first aspect of the application provides a two-component polyurethane waterproof coating composition comprising a component A and a component B, wherein the component A comprises isocyanate-terminated polyurethane, and the raw material components of the isocyanate-terminated polyurethane comprise polyether polyol, hydroxyl-terminated polybutadiene acrylonitrile and isocyanate, and the isocyanate is at least one selected from diisocyanate or polyisocyanate; the component B comprises 8-15 parts by mass of a plasticizer, a curing agent, 80-160 parts by mass of pigment filler, 5-10 parts by mass of tackifier and 0.1-0.3 part by mass of dispersing agent, relative to 100 parts by mass of plasticizer, 0.5-1.5 parts by mass of catalyst and selected from a carbamate catalyst and/or an allophanate catalyst, relative to 100 parts by mass of plasticizer, wherein the content of the curing agent is 8-15 parts by mass of pigment filler, relative to 100 parts by mass of plasticizer; the mixing mass ratio of the component A to the component B is 1:1-1:4.

Without intending to be limited by any theory or explanation, in the two-component polyurethane waterproof coating composition of the present application, the isocyanate-terminated polyurethane is obtained by reacting polyether polyol, hydroxyl-terminated polybutadiene acrylonitrile and isocyanate, and the segment structure of the hydroxyl-terminated polybutadiene acrylonitrile can effectively reduce the surface energy of the coating system, balance the polarity of the coating system, promote the affinity of the coating film to low-surface energy materials and low-polarity materials, and in addition, the cyano group introduced by the hydroxyl-terminated polybutadiene acrylonitrile can further improve the adhesive property of the coating system. In the two-component polyurethane waterproof coating composition, when the content of each component of the component B is in a proper range, the component A and the component B are mixed according to a proper proportion and then are constructed, and isocyanate-terminated polyurethane in the component A reacts with a curing agent in the component B to form a coating film. The coating film not only has good flexibility and air tightness, but also has low surface energy and good compatibility with low surface energy materials. Therefore, when the two-component polyurethane waterproof coating composition is applied to the composite construction of waterproof coating and asphalt waterproof coiled materials, the formed waterproof coating layer can have good compatibility and excellent bonding performance on the isolating film of the asphalt waterproof coiled materials. Therefore, the step of uncovering the film or using open fire to burn and fuse can be omitted during construction, and cold construction is directly performed, so that the construction efficiency is improved, and meanwhile, the composite waterproof performance of the asphalt waterproof coiled material and the paint layer is further improved.

In any of the embodiments of the first aspect of the present application, the content of the hydroxyl-terminated polybutadiene acrylonitrile is 30 to 80 parts by mass relative to 100 parts by mass of the polyether polyol, and the content of the isocyanate is 18 to 35 parts by weight relative to the polyether polyol.

Preferably, the polyether polyol comprises a difunctional polyether polyol and a trifunctional polyether polyol, and the mass ratio of the difunctional polyether polyol to the trifunctional polyether polyol is 1:0.4-1:0.8.

In any embodiment of the first aspect of the present application, the hydroxyl-terminated polybutadiene acrylonitrile has a number average molecular weight of 2000 to 3500 and a hydroxyl number of 0.50 to 0.80mmol/g.

In any embodiment of the first aspect of the present application, the isocyanate is selected from one or more of an aromatic diisocyanate or an aliphatic diisocyanate. Preferably, the isocyanate is selected from one or more of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate or tetramethyl m-xylylene diisocyanate.

In any embodiment of the first aspect of the present application, the plasticizer is selected from one or more of polyisobutylene, trioctyl phosphate, citrate, chlorinated paraffin, or phthalate plasticizers.

In any embodiment of the first aspect of the present application, the curing agent is selected from one or more of ethylene glycol, 1, 4-butanediol, trimethylolpropane, glycerol, triethanolamine, diethanolamine, 3 '-dichloro-4, 4' -diaminodiphenylmethane, toluenediamine, 4 '-methylene-bis (3-chloro-2, 6-diethylaniline), 4' -bis-sec-butylaminodiphenylmethane, diethyltoluenediamine, dimethylthiotoluenediamine and methylcyclohexamethylenediamine.

In any embodiment of the first aspect of the present application, the pigment and filler is selected from one or more of nano calcium carbonate, talc, fumed silica, heavy calcium, kaolin, silica micropowder, carbon black.

In any embodiment of the first aspect of the present application, the tackifier is selected from one or more of C5 petroleum resin, C9 petroleum resin, rosin modified resin, terpene resin, coumarone resin, copolymer resin, hydrogenated petroleum resin, modified petroleum resin.

In any embodiment of the first aspect of the present application, the catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, lead isooctanoate, zinc bismuth composite catalyst, bismuth isooctanoate, and zinc neodecanoate.

In any embodiment of the first aspect of the present application, the dispersant is selected from anionic wetting dispersants.

In any embodiment of the first aspect of the present application, the plasticizer is selected from polyisobutylene.

A second aspect of the present application provides a process for preparing the two-part polyurethane waterproofing coating composition of the first aspect of the present application, comprising:

preparing a component A, namely performing polycondensation reaction on polyether polyol, hydroxyl-terminated polybutadiene acrylonitrile and isocyanate at a reaction temperature to obtain the component A comprising isocyanate-terminated polyurethane;

the preparation of the component B comprises the steps of uniformly mixing a plasticizer, a curing agent, pigment and filler, a tackifier, a dispersing agent and a catalyst under the heating condition, so as to obtain the component B.

In any of the embodiments of the second aspect of the present application, the preparation of component B comprises:

mixing a plasticizer with a dispersant to obtain a first mixture;

uniformly mixing and dehydrating the first mixture, pigment filler and tackifier at a first temperature and under vacuum conditions to obtain a second mixture, wherein the first temperature is 100-110 ℃;

uniformly mixing the second mixture and a curing agent at a first temperature to obtain a third mixture;

And uniformly mixing the third mixture and the catalyst at a second temperature to obtain a component B after cooling, wherein the second temperature is 65-75 ℃.

A third aspect of the present application provides a structure comprising a water-repellent coating formed from the two-component polyurethane water-repellent coating composition of the first aspect of the present application, or a water-repellent coating formed from the two-component polyurethane water-repellent coating composition prepared according to the method of the second aspect of the present application.

In any embodiment of the third aspect of the present application, the waterproof coating comprises a first surface and a second surface opposite to the first surface, the structure further comprises an asphalt waterproof roll located on the first surface, the asphalt waterproof roll comprises a protective film far from the first surface, a separation film close to the first surface, and an asphalt layer located between the protective film and the separation film.

In any embodiment of the third aspect of the present application, the structure further comprises an epoxy primer layer on the second surface.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly describe the drawings that are required to be used in the embodiments of the present application; it is apparent that the figures described below relate only to some embodiments of the present application and that other figures can be obtained from the figures without inventive effort for a person of ordinary skill in the art.

FIG. 1 is a schematic view of a structure according to an embodiment of the present application

Fig. 2 is a schematic view of yet another structure provided in an embodiment of the present application.

Reference numerals illustrate:

100 structure; 110 a waterproof coating; 111 a first surface; 112 a second surface; 120 asphalt waterproof coiled materials; 121 a protective film; 122 a separation film; 123 asphalt layers; 130 epoxy primer

Detailed Description

In order to make the application purposes, technical solutions and beneficial technical effects of the present application clearer, the present application is further described in detail below with reference to examples. It should be understood that the embodiments described in this specification are for purposes of illustration only and are not intended to limit the present application.

For simplicity, only a few numerical ranges are explicitly disclosed in this application. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each point or individual value between the endpoints of the range is included within the range, although not explicitly recited. Thus, each point or individual value may be combined as a lower or upper limit on itself with any other point or individual value or with other lower or upper limit to form a range that is not explicitly recited.

In the description of the present application, unless otherwise indicated, "above" and "below" are intended to include the present number, and the meaning of "multiple" in "one or more" means two or more.

The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. Guidance is provided throughout this application by a series of embodiments, which may be used in various combinations. In the various examples, the list is merely a representative group and should not be construed as exhaustive.

As described in the background art, under the condition of the composite use of the waterproof coating and the asphalt waterproof coiled material, the problem of high difficulty in stripping the isolating film exists, and the asphalt layer is directly contacted with the coating layer, so that components of the asphalt layer and the coating layer can migrate and separate out, and the waterproof performance is reduced.

In the related art, the asphalt layer or the paint layer is modified from the standpoint of reducing the direct adhesion between the barrier film and the asphalt layer or improving the compatibility between the asphalt layer and the paint layer. However, the asphalt layer and the paint layer have complex components, so that the difficulty of modification is high, and the ideal effect is difficult to achieve.

The inventors have intensively studied and found that: the step of uncovering the film is omitted during construction, and the asphalt waterproof coiled material is directly paved on the surface of the paint layer, so that on one hand, the construction working procedures can be reduced, and the construction efficiency can be improved; on the other hand, the isolating film can play a role in blocking, and the paint layer is prevented from being in direct contact with the asphalt layer, so that migration and precipitation of components of the asphalt layer and the paint layer are prevented. In addition, the isolating film can also play a role in water resistance, so that the composite water resistance of the asphalt waterproof coiled material and the paint layer is further improved.

However, most of the existing coating layers are polyurethane waterproof coating layers with high polarity and high surface energy, and the coating has poor adhesion performance to the isolating film of the asphalt waterproof coiled material, so that the isolating film is difficult to wet and effectively adhere.

In view of this, the inventors have conducted intensive studies and a great deal of experiments to provide a two-component polyurethane waterproof coating material, a method for preparing the same, and a structure using the two-component polyurethane waterproof coating material composition.

The first aspect of the application provides a two-component polyurethane waterproof coating composition, which comprises a component A and a component B. Wherein the component A comprises isocyanate-terminated polyurethane, and the raw material component of the isocyanate-terminated polyurethane comprises polyether polyol, hydroxyl-terminated polybutadiene acrylonitrile and isocyanate, and the isocyanate is at least one selected from diisocyanate or polyisocyanate. The component B comprises 8-15 parts by mass of plasticizer, a curing agent, 80-160 parts by mass of pigment filler, 5-10 parts by mass of tackifier and 0.1-0.3 part by mass of dispersing agent, relative to 100 parts by mass of plasticizer, and 0.5-1.5 parts by mass of catalyst, relative to 100 parts by mass of plasticizer, wherein the content of the curing agent is 80-160 parts by mass of pigment filler, the content of the tackifier is 5-10 parts by mass of plasticizer, the content of the dispersing agent is 0.5-1.5 parts by mass of catalyst is urethane catalyst and/or allophanate catalyst. The mixing mass ratio of the component A to the component B is 1:1-1:4.

The hydroxyl-terminated polybutadiene acrylonitrile refers to polybutadiene acrylonitrile with-OH as two end groups in a molecular chain. Polyether polyols are oligomers whose main chain contains ether linkages (-R-O-R-), and whose end groups or side groups contain greater than or equal to 2 hydroxyl groups (-OH). The isocyanate-terminated polyurethane refers to polyurethane with isocyanate groups at least at two end groups in a molecular chain.

The above-mentioned urethanization catalyst means a catalyst which can be used for catalyzing the reaction for producing the urethane compound, and has a meaning well known in the art, and a specific kind thereof may be selected according to need and is not limited thereto. The allophanatization catalyst is a catalyst which can be used for catalyzing the reaction for producing allophanate compounds, and has a meaning known in the art, and the specific type thereof can be selected as desired without limitation.

Without intending to be limited by any theory or explanation, in the two-component polyurethane waterproof coating composition of the present application, the isocyanate-terminated polyurethane is obtained by reacting polyether polyol, hydroxyl-terminated polybutadiene acrylonitrile and isocyanate, and the segment structure of the hydroxyl-terminated polybutadiene acrylonitrile can effectively reduce the surface energy of the coating system, balance the polarity of the coating system, promote the affinity of the coating film to low-surface energy materials and low-polarity materials, and in addition, the cyano group introduced by the hydroxyl-terminated polybutadiene acrylonitrile can further improve the adhesive property of the coating system. In the two-component polyurethane waterproof coating composition, when the content of each component of the component B is in a proper range, the component A and the component B are mixed according to a proper proportion and then are constructed, and isocyanate-terminated polyurethane in the component A reacts with a curing agent in the component B to form a coating film. The coating film not only has good flexibility and air tightness, but also has low surface energy and good compatibility with low surface energy materials. Therefore, when the two-component polyurethane waterproof coating composition is applied to the composite construction of waterproof coating and asphalt waterproof coiled materials, the formed waterproof coating layer can have good compatibility and excellent bonding performance on the isolating film of the asphalt waterproof coiled materials. Therefore, the step of uncovering the film or using open fire to burn and fuse the isolating film can be omitted during construction, and cold construction is directly carried out, so that the construction efficiency is improved, and meanwhile, the composite waterproof performance of the asphalt waterproof coiled material and the paint layer is further improved.

In some embodiments, the hydroxyl-terminated polybutadiene acrylonitrile may be present in an amount of 30 to 80 parts by mass relative to 100 parts by mass of the polyether polyol and the isocyanate may be present in an amount of 18 to 35 parts by weight relative to the polyether polyol.

Without intending to be limited by any theory or explanation, the hydroxyl-terminated polybutadiene acrylonitrile, polyether polyol, isocyanate content, when within the above-described suitable ranges, can be such that the isocyanate-terminated polyurethane has a suitable molecular weight and cyano content. When the polyurethane has a suitable molecular weight, the polyurethane film-forming resin can have not only a suitable molecular weight and a degree of crosslinking but also a low polarity in the formed coating film, thereby enabling the coating film to have flexibility, air tightness and compatibility with the barrier film of the asphalt waterproof roll. When the polyurethane has a suitable cyano content, the formed coating film can have both the adhesive property of the isolating film of the asphalt waterproof coiled material and the adhesive property of the base surface, so that the composite waterproof property of the asphalt waterproof coiled material and the coating layer can be further improved.

Preferably, the polyether polyol may include a difunctional polyether polyol and a trifunctional polyether polyol, and the mass ratio of the difunctional polyether polyol to the trifunctional polyether polyol may be 1:0.4 to 1:0.8.

The above-mentioned bifunctional polyether polyol may represent a polyether polyol containing two hydroxyl groups in one molecule, and by way of example, the bifunctional polyether polyol may include, but is not limited to, polyether polyol DL-2000D or polyether polyol DL-1000.

The above-mentioned trifunctional polyether polyol may represent a polyether polyol containing three hydroxyl groups in one molecule, and by way of example, the trifunctional polyether polyol may include, but is not limited to, polyether polyol EP330N or polyether polyol MN1000.

Without intending to be limited by any theory or explanation, when the polyether polyol comprises a difunctional polyether polyol and a trifunctional polyether polyol in the above-described ranges, the polyurethane in the a-component can have suitable hydroxyl functionality. Therefore, in a coating film formed by the two-component polyurethane waterproof coating composition, the polyurethane film-forming resin can have proper crosslinking density, so that the coating film has good flexibility and high strength.

In some embodiments, the hydroxyl-terminated polybutadiene acrylonitrile may have a number average molecular weight of 2000 to 3500 and a hydroxyl number of 0.50 to 0.80mmol/g.

Without intending to be limited by any theory or explanation, when the hydroxyl-terminated polybutadiene acrylonitrile has a number average molecular weight and a hydroxyl number within the above-described suitable ranges, the isocyanate-terminated polyurethane can have a suitable molecular weight, cyano content, and hydroxyl content. Therefore, in a coating film formed by the two-component polyurethane waterproof coating composition, polyurethane film-forming resin can have proper molecular weight, crosslinking degree, polarity and cyano content, so that the flexibility and air tightness of the coating film can be improved, the compatibility between the coating film and an isolating film of an asphalt waterproof coiled material and the adhesive force between the coating film and the isolating film of the asphalt waterproof coiled material can be improved, and the composite waterproof performance of the asphalt waterproof coiled material and a coating layer can be further improved.

In some embodiments, the isocyanate may be selected from one or more of an aromatic diisocyanate or an aliphatic diisocyanate. Preferably, the isocyanate may be selected from one or more of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate or tetramethyl-m-xylylene diisocyanate.

The isocyanate is selected from the diisocyanate, and the crosslinking structure and activity of the polyurethane film-forming resin in the coating can be further regulated, so that the two-component polyurethane waterproof coating composition has higher stability and operability, and the adhesive property of the coating is further improved.

In some embodiments, the plasticizer may be selected from one or more of polyisobutylene, trioctyl phosphate, citrate, chlorinated paraffin, or phthalate plasticizers.

The plasticizer selected from the above types is applied to the two-component polyurethane waterproof coating composition, which not only allows the two-component polyurethane waterproof coating composition to have proper cost, but also enables a coating film formed by the two-component polyurethane waterproof coating composition to have high strength and good displacement resistance or tensile property.

The type of curing agent is not limited in this application, and may include curing agents commonly used in the art that can undergo urethanization or allophanation with isocyanate groups. In some embodiments, the curing agent may be selected from one or more of ethylene glycol, 1, 4-butanediol, trimethylolpropane, glycerol, triethanolamine, diethanolamine, 3 '-dichloro-4, 4' -diaminodiphenylmethane (MOCA), toluenediamine, 4 '-methylene-bis (3-chloro-2, 6-diethylaniline), 4' -bis-sec-butylaminodiphenyl-methane, diethyltoluenediamine, dimethylthiotoluenediamine and methylcyclohexamethylenediamine.

The curing agent selected from the above types can enable a coating film formed by the two-component polyurethane waterproof coating composition to have proper curing speed and strength, and can alleviate the problem of foaming of the coating film caused by the release of carbon dioxide gas by the direct reaction of the two-component polyurethane waterproof coating composition with water vapor.

In some embodiments, the pigment and filler may be selected from one or more of nano calcium carbonate, talc, fumed silica, heavy calcium, kaolin, silica fume, and carbon black.

The pigment and filler selected from the above types can enable the coating film formed by the two-component polyurethane waterproof coating composition to have proper cost, strength, good corrosion resistance and durability.

In some embodiments, the tackifier may be selected from one or more of C5 petroleum resin, C9 petroleum resin, rosin modified resin, terpene resin, coumarone resin, copolymer resin, hydrogenated petroleum resin, modified petroleum resin.

Without intending to be limited by any theory or explanation, the adhesion promoters selected from the above classes are capable of enhancing the wettability, initial adhesion, and hold-up of the coating system, thereby further enhancing the adhesion between the coating layer formed from the two-component polyurethane waterproofing coating composition and the release film of the asphalt waterproofing membrane.

In some embodiments, the catalyst may be selected from one or more of dibutyltin dilaurate, stannous octoate, lead isooctanoate, zinc bismuth composite catalyst, bismuth isooctanoate, zinc neodecanoate.

In some embodiments, the dispersant may be selected from anionic wetting dispersants. For example, the dispersant may include, but is not limited to, sodium oleate (C ₁₇ H ₃₃ COONa) and the like, and sulfuric acid ester salts (e.g. ROSO ₃ Na) or sulfonates (e.g. RSO) ₃ Na)。

The dispersing agent selected from the above types can reduce the surface polarity of inorganic fillers such as pigment and filler after being wrapped and adsorbed on the surface of the filler, and has obvious wetting, dispersing and anti-settling effects. The two-component polyurethane waterproof coating system comprises the dispersing agent selected from the above types, so that the viscosity of the coating system can be reduced and the adhesive force of a coating film can be increased.

In some embodiments, the plasticizer may be selected from polyisobutylene.

The polyisobutene has excellent compatibility with a coating system and a separation film, and can improve the initial viscosity and the holding power, the ageing resistance, the low-temperature flexibility and the like of the coating when being added into the coating system, and can cooperate with a tackifier to further improve the compatibility of the coating system and the separation film of the asphalt waterproof coiled material and the ageing resistance of a coating film, so that a composite structure formed by the asphalt waterproof coiled material and the coating layer has excellent waterproof performance and durability.

A second aspect of the present application provides a process for preparing the two-part polyurethane waterproofing coating composition of the first aspect of the present application, comprising: step S10, preparing a component A, wherein the component A comprises polycondensing polyether polyol, hydroxyl-terminated polybutadiene acrylonitrile and isocyanate at a reaction temperature, so as to obtain the component A comprising isocyanate-terminated polyurethane.

In step S10, the reaction temperature may be adjusted according to the reaction conditions, and the relative vacuum degree of the system may be adjusted during the reaction, which is not limited herein. As an example, step S10 may specifically include: mixing polyether polyol and hydroxyl-terminated polybutadiene acrylonitrile, and dehydrating for 2-3 hours under the conditions of stirring at 100-110 ℃ and a relative vacuum degree of minus 0.08-minus 0.1 MPa; and (3) reducing the temperature to 70-80 ℃, gradually adding isocyanate, controlling the temperature to 80-85 ℃ for heat preservation reaction for 3-4 hours, and then cooling and discharging to obtain the component A.

The method further comprises a step S20 of preparing the component B, wherein the step S comprises the step of uniformly mixing the plasticizer, the curing agent, the pigment filler, the tackifier, the dispersing agent and the catalyst under the heating condition so as to obtain the component B.

The types and amounts of the hydroxyl-terminated polybutadiene acrylonitrile, polyether polyol, isocyanate-terminated polyurethane, plasticizer, curing agent, pigment filler, tackifier, dispersant are respectively defined in the first aspect of the present application, and are not described in detail herein.

In the method, the polyether polyol, the hydroxyl-terminated polybutadiene acrylonitrile and isocyanate are subjected to polycondensation reaction to generate isocyanate-terminated polyurethane in the component A, the chain segment structure of the hydroxyl-terminated polybutadiene acrylonitrile can effectively reduce the surface energy of a coating system, balance the polarity of the coating system, promote the affinity of a coating film to a low-surface-energy material and a weak-polarity material, and in addition, the cyano-group introduced by the hydroxyl-terminated polybutadiene acrylonitrile can further improve the adhesive property of the coating system. The method also prepares the component B by mixing the components with proper types and proportions, thus the component A and the component B are mixed according to proper proportions and then are constructed, and the isocyanate-terminated polyurethane in the component A forms a coating film through the action of the curing agent in the component B. The coating film not only has good flexibility and air tightness, but also has low surface energy and good compatibility with low surface energy materials. Therefore, when the two-component polyurethane waterproof coating composition prepared by the method is applied to the composite construction of waterproof coating and asphalt waterproof coiled material, the formed waterproof coating layer can have good compatibility and excellent adhesive property on the isolating film of the asphalt waterproof coiled material. Therefore, the step of uncovering the film or using open fire to burn and fuse can be omitted during construction, and cold construction is directly performed, so that the construction efficiency is improved, and meanwhile, the composite waterproof performance of the asphalt waterproof coiled material and the paint layer is further improved.

In some embodiments, preparing component B may comprise:

uniformly mixing a plasticizer and a dispersing agent to obtain a first mixture;

The vacuum condition may be a vacuum or a state close to vacuum, and the vacuum condition may be, for example, a relative vacuum degree of between-0.08 and-0.1 MPa.

In the structure of the present application, the waterproof coating layer may be located on the surface of the base layer, and between the waterproof coating layer and the base layer, may further include optional other structural layers, and may further include other structural layers, for example, structural layers composed of waterproof rolls, on the surface of the waterproof coating layer away from the base layer. The base layer described herein may be cement concrete, cement mortar, cement paste, fiberboard, cement cushion layer, etc. at the locations of building roofs, basement floors, roofs, side walls, etc., or may be a building material such as a waterproof roll, but is not limited to the base layer listed above.

The structure of the application comprises a waterproof coating formed by a specific two-component polyurethane waterproof coating composition, and the waterproof coating not only has good flexibility and air tightness, but also has low surface energy and proper polarity, and has good compatibility with low surface energy materials. Therefore, the structure can be suitable for the non-polar surface and the non-polar surface, the polar surface and the non-polar surface, and can achieve good bonding waterproof effect.

FIG. 1 is a schematic diagram of one embodiment of a structure of the present application. The exemplary structure 100 includes a waterproof coating 110 and an asphalt waterproof roll 120. Wherein the waterproof coating layer 110 includes a first surface 111 and a second surface 112 opposite to the first surface 111, and the asphalt waterproof roll 120 includes a protective film 121 far from the first surface 111, a separation film 122 near the first surface, and an asphalt layer 123 between the protective film 111 and the separation film 122. As shown in fig. 1, in some embodiments, a separator 122 of an asphalt waterproofing membrane may be located on the first surface 111.

In the above-mentioned asphalt waterproof roll, the protective film may be a protective film known in the art to be applicable to asphalt waterproof rolls, and may be, for example, a PE film or a PET film. Among the above asphalt waterproofing rolls, the separator may be a separator known in the art to be useful for asphalt waterproofing rolls, and may include, for example, but not limited to, a separator formed of polyethylene PE, polyethylene terephthalate PET, ethylene-vinyl acetate copolymer EVA, thermoplastic polyurethane elastomer TPU, polyvinyl alcohol-thermoplastic polyurethane elastomer composite PVOH-TPU, and composite EVOH-TPU of ethylene-vinyl alcohol copolymer and thermoplastic polyurethane elastomer. In the above asphalt waterproof roll, the asphalt layer may be an asphalt layer known in the art to be useful for asphalt waterproof rolls, which may include a fetal asphalt layer or a non-fetal asphalt layer, which may be a modified or unmodified asphalt layer.

Without intending to be limited by any theory or explanation, the structures of the present application include a waterproof coating formed from a particular two-component polyurethane waterproof coating composition, which has low surface energy and suitable polarity, has good compatibility with a barrier film of an asphalt waterproof roll, and is capable of having high adhesion with the barrier film. Therefore, the risk of migration and precipitation caused by interaction of components in the asphalt layer and the waterproof coating can be reduced, the durability of the waterproof coating-waterproof coiled material composite structure is improved, and the waterproof performance of the structure can be further improved through the waterproof effect of the isolating film.

In some embodiments, as shown in fig. 2, structure 100 may further include an epoxy primer layer 130 on second surface 112.

The epoxy primer layer may be a primer layer formed by mixing an epoxy resin and a curing agent and then coating the mixture. The epoxy resin may be an epoxy resin well known in the art, which may be a modified or unmodified epoxy resin, and may include, for example, an E51 type epoxy resin, an E44 type epoxy resin, and the like. The curing agent may be an epoxy curing agent well known in the art, for example, an amine curing agent.

In the above embodiments, the epoxy primer layer may be located on the surface of the base layer. The epoxy primer can be directly formed on a wet base surface through epoxy coating in a construction mode, and has high adhesion with the waterproof coating of the application, so that the structure of the application can be formed in a wet environment, and the applicability and construction convenience of the structure are improved.

Examples

The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the examples below are by weight, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.

The sources of the raw materials used in the following examples are as follows:

hydroxyl-terminated polybutadiene acrylonitrile: the number average molecular weight is 2000-3500, the hydroxyl value is 0.50-0.80 mmol/g, purchased from Shandong Zibolong chemical industry Co., ltd;

Difunctional polyether polyol DL-2000D: functionality 2, number average molecular weight 2000, available from Shandong Lanxing Dong Co., ltd;

difunctional polyether polyol DL-1000: functionality 2, number average molecular weight 1000, available from Shandong Lanxing Dong Co., ltd;

trifunctional polyether polyols EP330N: functionality 3, number average molecular weight 5000, available from Shandong Lanxing Dong Co., ltd;

trifunctional polyether polyol MN1000: functionality 3, number average molecular weight 1000, available from Shandong Lanxing Dong Co., ltd;

polyisobutene: PB450 (molecular weight 450, viscosity 14.+ -.2 cst), available from Shanghai chemical Co., ltd;

dispersing agent: BYK-203, available from Toyang chemical Co., ltd;

pigment and filler: talc (1250 mesh), available from Corp;

tackifier: c9 petroleum resin, model BT-C90, available from Kyoang KRuider petroleum resin Co.

Other raw materials not specifically described are all common commercial products.

Example 1

Preparation of component A

Gradually adding 30 parts by mass of hydroxyl-terminated polybutadiene acrylonitrile and 100 parts by mass of polyether polyol into a reaction kettle;

stirring is started, the temperature is raised to 100-110 ℃, and the dehydration is carried out for 2-3 hours under the relative vacuum degree of minus 0.08 to minus 0.1 MPa;

Reducing the temperature to 70-80 ℃, gradually adding 18 parts by mass of toluene diisocyanate, controlling the temperature to 80-85 ℃ and preserving heat for reaction for 3-4 hours;

cooling to below 50 ℃, charging nitrogen for protection, and discharging to obtain the component A.

The polyether polyol comprises a difunctional polyether polyol DL-2000D and a trifunctional polyether polyol EP330N, and the mass ratio of the difunctional polyether polyol to the trifunctional polyether polyol is 1:0.4.

Preparation of component B

100 parts by mass of polyisobutene serving as a plasticizer and 0.1 part by mass of BYK-203 are put into a reaction kettle;

starting stirring, starting heating, gradually adding 80 parts by mass of 1250-mesh talcum powder and 5 parts by mass of BT-C90 into a reaction kettle, heating to 100-110 ℃, and dehydrating for 2-3 hours under the condition that the relative vacuum degree is minus 0.08-minus 0.1 MPa;

stopping vacuum, discharging vacuum to zero, adding 8 parts by mass of curing agent MOCA into the reaction kettle, and keeping the temperature at 100-110 ℃ for continuous reaction for 0.5-1 hour;

reducing the temperature to 65-75 ℃, adding 0.5 part by mass of catalyst dibutyltin dilaurate, and continuing stirring for reaction for 0.5-1 hour;

cooling to below 50 ℃, and discharging to obtain the component B.

The mixing mass ratio of the component A to the component B is 1:2.

Example 2

Based on the preparation process of example 1, the contents of the respective components in the preparation process were adjusted to prepare the A component and the B component of example 2. Specifically, the amount of hydroxyl-terminated polybutadiene acrylonitrile was adjusted to 50 parts by mass, toluene diisocyanate was adjusted to 25 parts by mass, BYK-203 was adjusted to 0.2 part by mass, talc was adjusted to 120 parts by mass, BT-C90 was adjusted to 8 parts by mass, curing agent was adjusted to 12 parts by mass, and catalyst was adjusted to 1 part by mass.

In example 2, the mixing mass ratio of the A component and the B component was 1:2.

Example 3

Based on the preparation process of example 1, the contents of the respective components in the preparation process were adjusted to prepare the A and B components of example 3. Specifically, the amount of hydroxyl-terminated polybutadiene acrylonitrile was adjusted to 80 parts by mass, toluene diisocyanate was adjusted to 35 parts by mass, BYK-203 was adjusted to 0.3 part by mass, talc was adjusted to 160 parts by mass, BT-C90 was adjusted to 10 parts by mass, curing agent was adjusted to 15 parts by mass, and catalyst was adjusted to 1.5 parts by mass.

In example 3, the mixing mass ratio of the A component and the B component was 1:2.

Example 4

Based on the preparation procedure of example 1, the mass ratio of the difunctional polyether polyol to the trifunctional polyether polyol was adjusted to 1:0.8 to prepare the A and B components of example 4.

In example 4, the mixing mass ratio of the A component and the B component was 1:2.

Examples 5 to 6

Based on the preparation process of example 3, the A and B components of examples 5 to 6 were prepared, respectively.

In example 5, the mixing mass ratio of the A component and the B component was 1:1.

In example 6, the mixing mass ratio of the A component and the B component was 1:4.

Example 7

Based on the preparation procedure of example 3, the difunctional polyether polyol was adjusted to be a difunctional polyether polyol DL-1000 and the trifunctional polyether polyol was a trifunctional polyether polyol MN1000, and the A and B components of example 7 were prepared.

In example 7, the mixing mass ratio of the A component and the B component was 1:2.

Example 8

Based on the procedure of example 3, the A and B components of example 8 were prepared by replacing toluene diisocyanate with an equivalent amount of hexamethylene diisocyanate, MOCA with an equivalent amount of 1, 4-butanediol, and dibutyltin dilaurate with an equivalent amount of zinc bismuth composite catalyst.

In example 8, the mixing mass ratio of the A component and the B component was 1:2.

Example 9

Based on the procedure of example 3, polyisobutene was replaced with an equal amount of chlorinated paraffin, and components A and B of example 9 were prepared.

In example 9, the mixing mass ratio of the A component and the B component was 1:2.

Example 10

Based on the procedure of example 3, the polyisobutene was replaced with an equal amount of trioctyl phosphate to prepare the A and B components of example 10.

In example 10, the mixing mass ratio of the A component and the B component was 1:2.

Example 11

Based on the preparation process of example 3, 100 parts by mass of polyisobutylene was replaced with 50 parts by mass of polyisobutylene and 50 parts by mass of chlorinated paraffin, the a and B components of example 11 were prepared.

In example 11, the mixing mass ratio of the A component and the B component was 1:2.

Comparative example 1

Based on the procedure of example 3, the hydroxy-terminated polybutadiene acrylonitrile was replaced with an equal amount of difunctional polyether polyol DL-2000D to prepare components A and B of comparative example 1.

In comparative example 1, the mixing mass ratio of the A component and the B component was 1:2.

Comparative example 2

Based on the procedure of example 3, the hydroxyl-terminated polybutadiene acrylonitrile was replaced with an equivalent amount of difunctional polyether polyol DL-2000D, and the polyisobutylene was replaced with an equivalent amount of chlorinated paraffin, to prepare components A and B of comparative example 2.

In comparative example 2, the mixing mass ratio of the A component and the B component was 1:2.

Comparative example 3

Based on the preparation procedure of example 3, the A and B components of comparative example 3 were prepared without adding polyisobutylene.

In comparative example 3, the mixing mass ratio of the A component and the B component was 1:2.

Comparative example 4

Based on the preparation procedure of example 3, the A and B components of comparative example 4 were prepared without adding BT-C90.

In comparative example 4, the mixing mass ratio of the A component and the B component was 1:2.

Test part

Surface dry time test

Testing according to the test standard in GB/T19250-2013 to obtain the surface dry time T ₁ 。

Real dry time test

Testing according to the test standard in GB/T19250-2013 to obtain the real dry time T ₂ 。

Elongation at break test

Testing was performed according to the test standard in GB/T19250-2013.

Tensile Strength test

Testing was performed according to the test standard in GB/T19250-2013.

Tear Strength test

Testing was performed according to the test standard in GB/T19250-2013.

Adhesive strength test

Testing was performed according to the test standard in GB/T19250-2013.

Impermeability test

Testing was performed according to the test standard in GB/T19250-2013.

PE isolation film coiled material composite peel strength test

Test piece size and preparation: cutting the asphalt waterproof coiled material, and keeping the size of the bonding surface of the asphalt waterproof coiled material to be 70 mm or 50mm; coating or spraying epoxy primer on the surface of the cement mortar block and curing for 24 hours at room temperature; uniformly mixing the two-component polyurethane waterproof coating composition according to the proportion, and coating the mixture on the surface of an epoxy primer, wherein the coating thickness is 1.5+/-0.2 mm; directly paving the cut coiled material with the isolating film on the polyurethane waterproof paint in the paint adaptation period, and compacting to enable the coiled material and the paint to be in a full-adhesion state; and curing the prepared test piece for 168 hours under standard curing conditions (the temperature is 23+/-2 ℃ and the relative humidity is 50+/-10%) to obtain the test piece.

And (3) mounting the cement mortar block surface in the test piece on a clamp at one end of an electronic tensile testing machine, and bending 180 the unbonded surface of the coiled material in the test piece, which is opposite to the bonding surface, in the clamp at the other end of the testing machine. Care was taken to accurately position the test piece between the jaws to ensure that the applied tension was evenly distributed across the width of the test piece. Starting the detection equipment, and setting the stretching speed to be 100mm/min. The maximum peel force is divided by the width of the test piece to obtain the composite peel strength T of the PE isolating film coiled material, wherein the composite peel strength T is in N/mm. The interface after peeling was observed, and the peeling failure form was determined.

The test results of examples 1 to 11 and comparative examples 1 to 4 are shown in Table 1, respectively.

TABLE 1

As can be seen from the results of table 1, the coating film formed from the two-component polyurethane waterproof coating composition of the present application has not only good flexibility, high strength and high adhesion properties, but also good compatibility with the nonpolar barrier film and high interfacial adhesion. In particular, when polyisobutylene is used as a plasticizer, the adhesion between a coating film formed by the two-component polyurethane waterproof coating composition and a nonpolar isolating film can be remarkably improved.

In contrast, comparative examples 1 and 2 did not use hydroxyl-terminated polybutadiene acrylonitrile during the preparation of the two-component polyurethane waterproof coating composition, and the interfacial adhesion between the coating film formed from the prepared two-component polyurethane waterproof coating composition and the nonpolar barrier film was significantly reduced. In particular, in comparative example 2, after the polyisobutylene was replaced with an equivalent amount of chlorinated paraffin, the peel strength was reduced to 0.64N/mm, which was far from meeting the cold construction requirements. Comparative examples 3 and 4 used hydroxyl-terminated polybutadiene acrylonitrile in the preparation of the two-component polyurethane waterproof coating composition, the prepared coating film formed by the two-component polyurethane waterproof coating composition had good flexibility and higher strength, but the interface adhesion between the formed coating film and the nonpolar barrier film was also significantly reduced without adding polyisobutylene and tackifier at the same time in comparative examples 3 and 4.

While the invention has been described with reference to certain preferred embodiments, it will be understood by those skilled in the art that various changes and substitutions of equivalents may be made and equivalents will be apparent to those skilled in the art without departing from the scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.

Claims

1. A two-component polyurethane waterproof coating composition capable of having good compatibility and excellent adhesion performance to a barrier film of an asphalt waterproof coiled material comprises a component A and a component B, wherein,

the component A comprises isocyanate-terminated polyurethane, wherein the raw material component of the isocyanate-terminated polyurethane comprises polyether polyol, hydroxyl-terminated polybutadiene acrylonitrile and isocyanate, the isocyanate is at least one of polyisocyanates, and the content of the hydroxyl-terminated polybutadiene acrylonitrile is 30-80 parts by mass relative to 100 parts by mass of the polyether polyol;

the component B comprises 8-15 parts by mass of a plasticizer, a curing agent, 80-160 parts by mass of pigment filler, 5-10 parts by mass of tackifier, 0.1-0.3 part by mass of dispersing agent and 0.5-1.5 parts by mass of catalyst, wherein the content of the curing agent is 8-15 parts by mass of the plasticizer, the content of the pigment filler is 80-160 parts by mass of the plasticizer, the content of the tackifier is 5-10 parts by mass of the plasticizer, the content of the dispersing agent is 0.5-1.5 parts by mass of the plasticizer, and the content of the catalyst is 0.5-1.5 parts by mass of the plasticizer, and the catalyst is selected from a carbamate catalyst and/or an allophanate catalyst;

The mixing mass ratio of the component A to the component B is 1:1-1:4.

2. The two-component polyurethane waterproof coating composition according to claim 1, wherein the isocyanate content is 18 to 35 parts by weight relative to the polyether polyol.

3. The two-component polyurethane waterproof coating composition according to claim 1, wherein the polyether polyol comprises a difunctional polyether polyol and a trifunctional polyether polyol, and the mass ratio of the difunctional polyether polyol to the trifunctional polyether polyol is 1:0.4-1:0.8.

4. The two-component polyurethane waterproof coating composition according to any one of claims 1 to 3, wherein the hydroxyl-terminated polybutadiene acrylonitrile has a number average molecular weight of 2000 to 3500 and a hydroxyl value of 0.50 to 0.80mmol/g; and/or

The isocyanate is one or more selected from aromatic diisocyanate or aliphatic diisocyanate.

5. A two-part polyurethane waterproofing coating composition according to any one of claims 1 to 3 wherein the isocyanate is selected from one or more of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate or tetramethyl-m-xylylene diisocyanate.

6. A two-component polyurethane waterproofing coating composition according to any one of claims 1 to 3 wherein the plasticizer is selected from one or more of polyisobutylene, trioctyl phosphate, citrate, chlorinated paraffin or phthalate plasticizers; and/or

The curing agent is selected from one or more of ethylene glycol, 1, 4-butanediol, trimethylolpropane, glycerol, triethanolamine, diethanolamine, 3 '-dichloro-4, 4' -diaminodiphenyl methane, toluenediamine, 4 '-methylene-bis (3-chloro-2, 6-diethylaniline), 4' -di-sec-butylamino-diphenyl methane, diethyl toluenediamine, dimethyl thiotoluenediamine and methylcyclohexane diamine; and/or

The pigment and filler is one or more selected from nano calcium carbonate, talcum powder, fumed silica, heavy calcium, kaolin, silica micropowder and carbon black; and/or

The tackifier is one or more selected from C5 petroleum resin, C9 petroleum resin, rosin modified resin, terpene resin, coumarone resin, copolymer resin, hydrogenated petroleum resin and modified petroleum resin; and/or

The catalyst is selected from one or more of dibutyl tin dilaurate, stannous octoate, lead isooctanoate, zinc bismuth composite catalyst, bismuth isooctanoate and zinc neodecanoate; and/or

The dispersant is selected from anionic wetting dispersants.

7. A two-part polyurethane waterproofing coating composition according to any one of claims 1 to 3 wherein the plasticizer is selected from polyisobutylene.

8. A process for preparing the two-part polyurethane waterproofing coating composition according to any one of claims 1 to 7 comprising:

preparing a component a comprising polycondensing said polyether polyol, said hydroxyl-terminated polybutadiene acrylonitrile, and said isocyanate at a reaction temperature to obtain said component a comprising an isocyanate-terminated polyurethane;

and preparing a component B, namely uniformly mixing the plasticizer, the curing agent, the pigment filler, the tackifier, the dispersing agent and the catalyst under the heating condition, so as to obtain the component B.

9. The method of claim 8, wherein said preparing said B component comprises:

mixing the plasticizer with the dispersant, thereby obtaining a first mixture;

uniformly mixing and dehydrating the first mixture, the pigment filler and the tackifier under the conditions of a first temperature and vacuum, so as to obtain a second mixture, wherein the first temperature is 100-110 ℃;

Uniformly mixing the second mixture and the curing agent at the first temperature to obtain a third mixture;

and uniformly mixing the third mixture and the catalyst at a second temperature to obtain the component B after cooling, wherein the second temperature is 65-75 ℃.

10. A structure comprising a water-repellent coating formed from the two-component polyurethane water-repellent coating composition according to any one of claims 1 to 7, or a water-repellent coating formed from the two-component polyurethane water-repellent coating composition prepared by the method according to claim 8 or 9.

11. The structure of claim 10, wherein the waterproof coating comprises a first surface and a second surface opposite the first surface, the structure further comprising an asphalt waterproof roll on the first surface, the asphalt waterproof roll comprising a protective film distal to the first surface, a barrier film proximal to the first surface, and an asphalt layer between the protective film and the barrier film.

12. The structure of claim 11, wherein the structure further comprises an epoxy primer layer on the second surface.