CN115386291B - Single-component polyurethane waterproof coating and preparation method thereof - Google Patents
Single-component polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- CN115386291B CN115386291B CN202211230417.8A CN202211230417A CN115386291B CN 115386291 B CN115386291 B CN 115386291B CN 202211230417 A CN202211230417 A CN 202211230417A CN 115386291 B CN115386291 B CN 115386291B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The application provides a single-component polyurethane waterproof coating and a preparation method thereof, wherein the single-component polyurethane waterproof coating comprises polyurethane film-forming resin, a filler and an additive; the polyurethane film-forming resin comprises a molecular chain skeleton obtained by reacting hydroxyl-terminated polybutadiene acrylonitrile, organic silicon diol, polyether polyol and diisocyanate and a blocking chain segment connected with the molecular chain skeleton; the end-capping chain segment has a chain segment structure represented by formula 1, wherein n is an integer of 1 to 25, and R is 1 Each occurrence is independently selected from hydrogen or a structure represented by formula 2, and at least one R 1 Is a structure represented by formula 2, wherein R in formula 2 2 、R 4 Each occurrence is independently selected from one of hydrogen or C1-C3 alkyl; r 3 Each occurrence is independently selected from hydrogen or C1-C8 alkyl or-R 3 'OH，R 3 ' is selected from C1-C8 alkylene; r 5 Selected from C1-C8 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from one of C1-C8 alkylene; r is 6 Each occurrence is independently selected from hydrogen or C1-C8 alkyl; m is an integer of 1 to 3.
Description
Technical Field
The application relates to the technical field of coatings, in particular to a single-component polyurethane waterproof coating and a preparation method thereof.
Background
The polyurethane waterproof paint is one of important components for the application of polyurethane synthetic materials. The coating film of the polyurethane coating has the characteristics of good elasticity and extensibility, good cohesiveness, small volume shrinkage, no seam of a waterproof layer of the coating film, strong adaptability to the deformation of the elasticity of cracks of a base layer, convenient construction and maintenance, easy construction on the surface of any base layer with a complex structure and the like, can be used for the water prevention and leakage stoppage of different parts of a building, and becomes one of main materials for building water prevention.
However, the application scenarios of the currently marketed single-component polyurethane waterproof coating in China are limited, for example, the coating is easy to absorb water and swell under a soaking condition to cause slow hydrolysis or degradation of the coating, and particularly, the coating is in poor adhesion conditions such as bulging, cracking and peeling caused by water absorption and swelling under a long-term soaking condition, so that the waterproof performance is finally failed, and the use requirements under underground high-temperature, high-humidity or long-term soaking environmental conditions cannot be met.
Disclosure of Invention
In view of the above, the application provides a single-component polyurethane waterproof coating and a preparation method thereof, so as to solve the problem that the adhesion and water immersion resistance of the existing polyurethane waterproof coating cannot meet the use requirements.
In one aspect, embodiments herein provide a one-component polyurethane waterproof coating including a polyurethane film-forming resin, a filler, and an additive; the polyurethane film-forming resin comprises a molecular chain skeleton obtained by reacting hydroxyl-terminated polybutadiene acrylonitrile, organic silicon dihydric alcohol, polyether polyol and diisocyanate, and a blocking chain segment connected with the molecular chain skeleton; the end-capping segment includes a segment structure represented by formula 1,
in the formula 1, n is an integer of 1 to 25,
R 1 each occurrence is independently selected from hydrogen or a structure represented by formula 2, and at least one R 1 In order to have the structure shown in formula 2,
in the formula 2, R 2 、R 4 Each occurrence is independently selected from hydrogen or C1-C3 alkyl;
R 3 each occurrence is independently selected from hydrogen or C1-C8 alkyl or-R 3 'OH，R 3 ' is selected from C1-C8 alkylene;
R 5 selected from C1-C8 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from one of C1-C8 alkylene;
R 6 each occurrence is independently selected from hydrogen or C1-C8 alkyl;
m is an integer of 1 to 3.
Alternatively, in formula 1, R 2 、R 4 Each occurrence is independently selected from hydrogen or CH 3 ，R 6 Each occurrence is independently selected from hydrogen or C1-C4 alkyl;
R 3 each occurrence is independently selected from hydrogen, C1-C4 alkyl or-R 3 One of' OH, R 3 ' is selected from C1-C4 alkylene;
R 5 independently at each occurrence, is selected from C1-C4 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from C1-C4 alkylene.
Alternatively, the polyurethane film-forming resin is obtained by reacting a polyurethane prepolymer with a capping agent;
the end-capping agent is bisphenol A type epoxy resin,
And &>
Under the initiation of a free radical initiator, wherein the bisphenol A type epoxy resin:
1-1;
the polyurethane prepolymer is obtained by reacting hydroxyl-terminated polybutadiene acrylonitrile, organic silicon dihydric alcohol, polyether polyol and diisocyanate.
Optionally, the bisphenol a type epoxy resin comprises at least one of E54, E51, E44, E42, E21, or E20; and/or
Optionally, the molecular weight of hydroxyl-terminated polybutadiene acrylonitrile is 2500-3500, and the hydroxyl value is 0.55-0.7mmol/g; and/or
The polyether polyol is selected from one or more of polyether diol and polyether triol; and/or
The organic silicon double-end dihydric alcohol comprises a compound shown as a formula 3, the number average molecular weight of the organic silicon double-end dihydric alcohol is 1000-4000,
wherein R is 7 Is selected from C1-C25 alkyl, a is selected from an integer of 8-50; and/or
The diisocyanate is selected from one or more of aromatic diisocyanate or aliphatic diisocyanate.
Optionally, the waterproof coating comprises the following raw material components in parts by weight:
100 parts of polyether polyol; 12-25 parts of hydroxyl-terminated polybutadiene acrylonitrile; 5-8 parts of organic silicon dihydric alcohol; 12-16 parts of diisocyanate; 12-18 parts of an end-capping agent; 23-42 parts of a filler; 8-15 parts of an additive.
Optionally, the filler comprises one or more of carbon black, titanium dioxide, kaolin, fumed silica, heavy calcium, barium sulfate, silica micropowder and talcum powder; and/or the additive comprises a plasticizer, and the plasticizer comprises one or more of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, trioctyl phosphate, citric acid ester and chlorinated paraffin.
In another aspect, embodiments of the present application provide a method for preparing a one-component polyurethane waterproof coating, including:
reacting 100 parts by weight of polyether polyol, 12-25 parts by weight of hydroxyl-terminated polybutadiene acrylonitrile, 5-8 parts by weight of organic silicon diol, 12-16 parts by weight of diisocyanate, a filler and an additive in an organic solvent in the presence of a catalytic amount of a catalyst for a urethanization reaction to obtain a first slurry;
the first sizing agent and 12-18 parts by weight of end-capping reagent react in the presence of a catalytic amount of catalyst for a urethanization reaction to obtain the single-component polyurethane waterproof coating, wherein the end-capping reagent has a structure shown as a formula 4,
in the formula 4, n is an integer of 1 to 25,
R 1 each occurrence is independently selected from hydrogen or a structure represented by formula 2, and at least one R 1 In order to have the structure shown in formula 2,
in the formula 2, R 2 、R 4 Each occurrence is independently selected from hydrogen or C1-C3 alkyl;
R 3 each occurrence is independently selected from hydrogen or C1-C8 alkyl or-R 3 'OH，R 3 ' is selected from C1-C8 alkylene;
R 5 selected from C1-C8 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from one of C1-C8 alkylene;
R 6 each occurrence is independently selected from hydrogen or C1-C8 alkyl;
m is an integer of 1 to 3.
Optionally, the catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate and lead isooctanoate.
Optionally, the method comprises:
the blocking agent was prepared by:
dissolving bisphenol A epoxy resin in a solvent to obtain an epoxy resin solution;
mixing an epoxy resin solution with
Mixing with a free radical initiator, reacting at the initiation temperature of the free radical initiator to obtain an end-capping agent, wherein, the bisphenol A type epoxy resin,
And &>
The molar ratio of (1).
Compared with the prior art, the application has at least the following beneficial effects:
the single-component polyurethane waterproof coating provided by the application comprises polyurethane film-forming resin formed by a blocking chain segment with a specific structure and a polyurethane prepolymer molecular chain framework, wherein the blocking chain segment contains an epoxy group, an acrylic acid chain segment/an acrylic ester chain segment and a siloxane group, the polyurethane prepolymer molecular chain framework contains a nitrile group and a siloxane structure, and the polyurethane film-forming resin formed by the polyurethane film-forming resin also contains the groups. On one hand, epoxy groups, nitrile groups, acrylic groups and the like can improve the adhesive capacity of the polyurethane film-forming resin. On the other hand, siloxane groups included in the end-capping chain segment of the polyurethane film-forming resin can not only enable the film-forming resin to have low surface energy, but also can be hydrolyzed to generate active hydroxyl groups, and the end hydroxyl groups are subjected to condensation crosslinking reaction and are also reacted with groups on the surface of the base material, so that the bonding capability of the polyurethane film-forming resin to the base material can be further improved, carbon dioxide gas is not released in the crosslinking curing process, a tight and pore-free coating is formed after curing, and the problems of poor bonding such as coating bulging, cracking and peeling caused by water absorption expansion of the coating under the water immersion condition are solved.
In addition, siloxane bonds contained in a molecular chain skeleton and a blocking chain segment reduce the surface energy of a polyurethane waterproof coating system, the low surface energy improves the hydrophobicity and the swelling resistance of a product, and the problem that the waterproof performance of a coating fails due to hydrolysis or degradation of the coating caused by water absorption expansion of a coating in the using process is solved.
Detailed Description
In order to make the application purpose, technical solution and beneficial technical effects of the present application clearer, the present application is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present application and are not intended to limit the present application.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value may, as its lower or upper limit, be combined with any other point or individual value or with other lower or upper limits to form ranges not explicitly recited.
In the description of the present application, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive of the present number, and "plural" of "one or more" means two or more.
Throughout this specification, substituents of compounds are disclosed in groups or ranges. It is expressly intended that such description include each individual sub-combination of members of these combination ranges. For example, the term "C1-C5 alkyl" is expressly contemplated to disclose separately C1, C2, C3, C4, C5, C1-C4, C1-C3, C1-C2, C2-C5, C2-C4, C2-C3, C3-C5, C3-C4, C4-C5 alkyl.
The term "alkylene" alone or as part of another substituent means a divalent radical derived from an alkyl group.
The single-component polyurethane waterproof paint has a wide development prospect, however, the application scenes of the single-component polyurethane waterproof paint sold on the market at home at present are limited, one part of the single-component polyurethane waterproof paint is easily influenced by construction environment after construction due to an adopted-NCO crosslinking curing system, so that the coating film has the problems of pinholes, foaming and the like, the later-stage coating film is easily subjected to the phenomena of bulging, water channeling and the like under the condition of water immersion, the other part of the single-component polyurethane waterproof paint adopts a conventional ketimine/aldimine latent curing agent, although the problems of air bubbles of a dry base surface and normal temperature and normal humidity can be solved, the coating film is easily subjected to water absorption expansion under the water immersion condition and cannot be directly constructed on a wet base surface, the coating film is easily subjected to water absorption expansion under the water immersion condition, the coating film is slowly hydrolyzed or degraded, particularly, the coating film is subjected to poor adhesion conditions such as bulging, cracking, stripping and the like under the long-term water immersion condition, and the waterproof performance is finally failed, and the use requirements under the underground high-temperature, high humidity or long-term water immersion environment condition can not be met.
In view of the above, the inventors have made extensive studies and experiments to provide a one-component polyurethane waterproof coating and a preparation method thereof.
In one aspect, embodiments herein provide a one-component polyurethane waterproof coating including a polyurethane film-forming resin, a filler, and an additive; the polyurethane film-forming resin comprises a molecular chain skeleton obtained by reacting hydroxyl-terminated polybutadiene acrylonitrile, organic silicon dihydric alcohol, polyether polyol and diisocyanate, and a blocking chain segment connected with the molecular chain skeleton; the end capping segment comprises a segment structure shown in formula 1,
in the formula 1, n is an integer of 1 to 25,
R 1 each occurrence is independently selected from hydrogen or a structure represented by formula 2, and at least one R 1 In order to have the structure shown in formula 2,
in the formula 2, R 2 、R 4 Each occurrence is independently selected from hydrogen or C1-C3 alkyl;
R 3 each occurrence is independently selected from hydrogen or C1-C8 alkyl or-R 3 'OH，R 3 ' is selected from C1-C8 alkylene;
R 5 selected from C1-C8 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from one of C1-C8 alkylene;
R 6 each occurrence is independently selected from hydrogen or C1-C8 alkyl;
m is an integer of 1 to 3.
The term "molecular chain skeleton" has the meaning known to the person skilled in the art. The polyurethane film-forming resin comprises a molecular chain skeleton of an isocyanate-terminated polyurethane prepolymer, and means that a molecular chain of the polyurethane film-forming resin comprises a main chain structure of the polyurethane prepolymer formed by the reaction of the specific reactants, wherein the molecular chain of the main chain structure comprises urethane groups and contains isocyanate end groups. Such polyurethane prepolymers can be reacted with blocking agents having isocyanate-reactive functional groups (e.g., hydroxyl groups) to introduce blocked segments having a specific structure (as shown in formula 1 above).
According to the embodiment of the application, the one-component polyurethane waterproof paint comprises a polyurethane film-forming resin formed by a blocking chain segment with a specific structure and a molecular chain framework of a polyurethane prepolymer, wherein the blocking chain segment contains an epoxy group, an acrylic acid chain/acrylate chain segment and a siloxane group, the molecular chain framework of the polyurethane prepolymer contains a nitrile group and a siloxane structure, and the polyurethane film-forming resin formed by the method also contains the groups. On one hand, epoxy groups, nitrile groups, acrylic groups and the like can improve the adhesive capacity of the polyurethane film-forming resin. On the other hand, siloxane groups included in the end-capping chain segment of the polyurethane film-forming resin can not only enable the film-forming resin to have low surface energy, but also can be hydrolyzed to generate active hydroxyl groups, and the end hydroxyl groups are subjected to condensation crosslinking reaction and are also reacted with groups on the surface of a base material, so that the bonding capacity of the polyurethane film-forming resin to the base material can be further improved, carbon dioxide gas is not released in the crosslinking curing process, a tight and pore-free coating is formed after curing, and the problems of coating film bulging, cracking, peeling and the like caused by water absorption expansion of the coating under the water immersion condition are solved.
According to the embodiment of the application, the siloxane bonds contained in the molecular chain skeleton and the end-capping chain segment reduce the surface energy of a polyurethane waterproof coating system, the hydrophobicity and the swelling resistance of a product are improved due to the low surface energy, and the problem that the waterproof performance of a coating fails due to the hydrolysis or degradation of the coating caused by water absorption expansion in the using process of the coating is avoided.
In some embodiments, in formula 1, R 2 、R 4 Each occurrence is independently selected from hydrogen or CH 3 ，R 6 Each occurrence is independently selected from hydrogen or C1-C4 alkyl;
R 3 each occurrence is independently selected from hydrogen, C1-C4 alkyl or-R 3 One of' OH, R 3 ' is selected from C1-C4 alkylene;
R 5 independently at each occurrence, is selected from C1-C4 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from C1-C4 alkylene.
In some embodiments, the polyurethane film-forming resin is derived from reacting a polyurethane prepolymer with a capping agent, wherein:
the end capping agent is bisphenol A type epoxy resin,
And
under the initiation of a free radical initiator, wherein the bisphenol A type epoxy resin: />
1-1;
the polyurethane prepolymer is obtained by reacting hydroxyl-terminated polybutadiene acrylonitrile, organic silicon dihydric alcohol, polyether polyol and diisocyanate.
In some embodiments, the bisphenol a-type epoxy resin includes at least one of E54, E51, E44, E42, E21, or E20.
In some embodiments of the present invention, the substrate is,
including one of methyl methacrylate, methacrylic acid, acrylic acid or hydroxyethyl methacrylate.
In some embodiments, at least one R is 5 Is composed of
R 5 ' and R 5 "is independently selected from C1-C4 alkylene.
In some embodiments of the present invention, the substrate is,
comprises one of gamma- (methacryloyloxy) propyl trimethoxy silane, alpha- (methacryloyloxy) methyl triethoxy silane, gamma- (methacryloyloxy) propyl tri (beta-methoxyethoxy) silane or N-methacryloyloxyethyl-N-dimethyl propyl trimethoxy silane hydrochloride.
In some embodiments, the hydroxyl-terminated polybutadiene acrylonitrile has a number average molecular weight of 2000 to 3500 and a hydroxyl value of 0.55 to 0.7mmol/g.
In some embodiments, the polyether polyol is selected from one or more of polyether diol, polyether triol.
Illustratively, polyether diols include DL-2000D and the like, and polyether triols include EP330N or MN1000 and the like. The polyether polyol has proper functionality, so that the molecular chain skeleton of the polyurethane film-forming resin has a proper cross-linking structure, and the single-component polyurethane waterproof coating composition has both water resistance and operability.
In some embodiments, the silicone double-ended diol comprises a compound represented by formula 3, the silicone double-ended diol has a number average molecular weight of 1000 to 4000,
wherein R is 7 Is selected from C1-C25 alkyl, a is selected from an integer of 8-50.
In some embodiments, the diisocyanate is selected from one or more of an aromatic diisocyanate or an aliphatic diisocyanate. The isocyanate may be selected from one or more of aromatic diisocyanate or aliphatic diisocyanate, and preferably, the diisocyanate may be selected from one or more of toluene diisocyanate, diphenylmethane-4, 4' -diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, and tetramethylm-xylylene diisocyanate.
In some embodiments, the waterproof coating comprises the following raw material components in parts by weight:
polyether polyol, 100 parts;
12-25 parts of hydroxyl-terminated polybutadiene acrylonitrile;
5-8 parts of organic silicon dihydric alcohol;
12-16 parts of diisocyanate;
12-18 parts of an end-capping agent;
23-42 parts of a filler;
8-15 parts of additive.
In some embodiments, the kind of the filler is not particularly limited, and may be selected according to actual needs. The filler includes one or more of carbon black, titanium dioxide, kaolin, fumed silica, heavy calcium, barium sulfate, silica micropowder, and talc powder, as examples.
In some embodiments, the additive includes a plasticizer, and the kind of the plasticizer is not particularly limited and may be selected according to actual needs. As an example, the plasticizer includes one or more of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, trioctyl phosphate, citric acid ester, and chlorinated paraffin.
In another aspect, embodiments of the present application provide a method for preparing a one-component polyurethane waterproof coating, including:
s10, reacting 100 parts by weight of polyether polyol, 12-25 parts by weight of hydroxyl-terminated polybutadiene acrylonitrile, 5-8 parts by weight of organic silicon diol, 12-16 parts by weight of diisocyanate, a filler and an additive in an organic solvent in the presence of a catalytic amount of a catalyst for a urethanization reaction to obtain first slurry;
s20, reacting the first slurry with 12-18 parts by weight of end-capping reagent in the presence of a catalytic amount of catalyst for a urethanization reaction to obtain the single-component polyurethane waterproof coating, wherein the end-capping reagent has a structure shown in a formula 4,
in the formula 4, n is an integer of 1 to 25,
R 1 each occurrence is independently selected from hydrogen or a structure represented by formula 2, and at least one R 1 In order to have the structure shown in formula 2,
in the formula 2, R 2 、R 4 Each occurrence is independently selected from hydrogen or C1-C3 alkyl;
R 3 each occurrence is independently selected from hydrogen or C1-C8 alkyl or-R 3 'OH，R 3 ' is selected from C1-C8 alkylene;
R 5 selected from C1-C8 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from one of C1-C8 alkylene;
R 6 each occurrence is independently selected from hydrogen or C1-C8 alkyl;
m is an integer of 1 to 3.
In step S10, the organic solvent includes, but is not limited to, one or more of toluene, xylene, tetramethylbenzene, trimethylbenzene, mineral spirit, ethyl acetate, butyl acetate, and propylene glycol methyl ether acetate.
In steps S10 and S20, the catalyst may be any catalyst known in the art and used for catalyzing the carbamate reaction, and the type and amount of the catalyst may be selected according to the specific reactants, which is not limited herein. Preferably, in step S10, the catalyst is used in an amount of 0.2 to 0.5 parts by weight; in step S20, the catalyst is used in an amount of 0.3 to 1.0 part by weight.
In step S10, the specific reaction conditions may be adjusted according to the actual amount of charge, and the like, and are not limited herein. As an example, the reaction temperature may be 75 ℃ to 85 ℃ and the reaction time may be 3 hours to 4 hours.
In some embodiments, step S10 may specifically include the following steps:
s11, uniformly dispersing hydroxyl-terminated polybutadiene acrylonitrile, organic silicon dihydric alcohol, polyether polyol, a filler and an additive to obtain mixed slurry;
s12, adding an organic solvent into the mixed slurry, gradually adding diisocyanate into the mixed slurry, stirring, heating to 75-85 ℃ in the presence of a catalytic amount of a catalyst for a carbamation reaction, and reacting for 3-4 hours to obtain a first slurry.
Preferably, in step S11, the hydroxyl-terminated polybutadiene acrylonitrile, the silicone diol, the polyether polyol, the filler and the additive are uniformly dispersed in an intensive disperser.
Preferably, in step S12, the diisocyanate dropping speed is controlled to be 1 to 2 parts by weight/S.
In some embodiments, before step S10 is performed, the polyether polyol, the hydroxyl-terminated polybutadiene acrylonitrile and the silicone diol may be dried and then reacted with the diisocyanate. Preferably, the polyether glycol, the hydroxyl-terminated polybutadiene acrylonitrile and the organic silicon dihydric alcohol are dehydrated for 2 to 3 hours under the conditions of 100 to 110 ℃ and the relative vacuum degree of-0.08 to-0.1 Mpa.
In step S20, the specific reaction conditions may be adjusted according to actual conditions, and are not limited herein. As an example, the reaction temperature of step S20 may be 75 to 85 ℃ and the reaction time may be 2.5 to 4 hours. In some embodiments, step S20 may specifically include the following steps:
s21, mixing and stirring the first slurry and an end-capping reagent at 75-85 ℃ for reaction for 2-3 hours;
s22, adding a catalytic amount of catalyst for the carbamation reaction at the temperature of between 50 and 60 ℃, and stirring for reaction for 0.5 to 1 hour;
and S23, cooling to below 50 ℃, and filling nitrogen for protection to obtain the single-component polyurethane waterproof coating.
According to embodiments of the present application, the method of preparation may be monitored according to any suitable method known in the art. For example, product formation can be monitored by spectroscopic means such as nuclear magnetic resonance spectroscopy (NMR, e.g., 1H or 13C), infrared spectroscopy (IR), spectrophotometry (e.g., UV visible), mass Spectrometry (MS), or by chromatography such as High Performance Liquid Chromatography (HPLC), gas Chromatography (GC), gel Permeation Chromatography (GPC), or Thin Layer Chromatography (TLC).
According to the method for preparing the one-component polyurethane waterproof coating composition, the obtained one-component polyurethane waterproof coating comprises a polyurethane film-forming resin formed by a blocking chain segment with a specific structure and a polyurethane prepolymer molecular chain skeleton, wherein the blocking chain segment contains an epoxy group, an acrylic acid chain segment/acrylic ester chain segment and a siloxane group, the polyurethane prepolymer molecular chain skeleton contains a nitrile group and a siloxane structure, and the polyurethane film-forming resin formed by the above groups also contains the groups. On one hand, epoxy groups, nitrile groups, acrylic groups and the like can improve the adhesive capacity of the polyurethane film-forming resin. On the other hand, siloxane groups included in the end-capping chain segment of the polyurethane film-forming resin can not only enable the film-forming resin to have low surface energy, but also can be hydrolyzed to generate active hydroxyl groups, and the end hydroxyl groups are subjected to condensation crosslinking reaction and are also reacted with groups on the surface of the base material, so that the bonding capability of the polyurethane film-forming resin to the base material can be further improved, carbon dioxide gas is not released in the crosslinking curing process, a tight and pore-free coating is formed after curing, and the problems of poor bonding such as coating bulging, cracking and peeling caused by water absorption expansion of the coating under the water immersion condition are solved. In addition, the surface energy of a polyurethane waterproof coating system is reduced by the contained siloxane bonds, the hydrophobicity and the swelling resistance of the product are improved by the low surface energy, and the problem that the waterproof performance of a coating fails due to hydrolysis or degradation of the coating caused by water absorption swelling in the use process of the coating is avoided.
In some embodiments, the catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, and lead isooctanoate.
In some embodiments, the method for preparing the one-component polyurethane waterproof coating further comprises:
the blocking agent was prepared by:
s31, dissolving bisphenol A epoxy resin in a solvent to obtain an epoxy resin solution;
s32, mixing the epoxy resin solution with
Mixing with free radical initiator, reacting at the initiation temperature of the free radical initiator to obtain end capping agent,
wherein, the bisphenol A type epoxy resin,
And &>
The molar ratio of (1).
In step S31, the specific dissolution temperature and dissolution time of the epoxy resin can be adjusted according to the actual type of epoxy resin, and is not limited herein. As an example, the dissolution temperature may be 80 ℃ to 90 ℃ and the dissolution time may be 3h to 4h. The solvent for dissolving the epoxy resin can be selected according to actual requirements. As an example, the solvent comprises a mixed solvent of n-butyl alcohol and ethylene glycol butyl ether, and the use amount of the mixed solvent of n-butyl alcohol and ethylene glycol butyl ether is 10-15% of the total mass of the reaction.
In step S32, the specific reaction temperature may be adjusted according to the actual radical initiator, which is not limited herein. As an example, the reaction temperature may be 90 ℃ to 95 ℃ and the reaction time may be 6 hours to 7 hours. The radical initiator may be any radical initiator known in the art, and the type and amount of the radical initiator may be selected according to the specific reactants, and is not limited herein. By way of example, the free radical initiator includes benzoyl peroxide.
In some embodiments, in step S32, after the reaction at the initiation temperature of the radical initiator, the step of evacuating and distilling under reduced pressure for 0.5 to 1 hour to obtain the end-capping reagent.
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 following examples are on a weight basis, 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 equipment used in the examples is commercially available.
The following examples used the following sources of starting materials:
hydroxyl-terminated polybutadiene acrylonitrile: the molecular weight of type IV of Shandong Zibo Qilong chemical Co., ltd is not less than 2500, and the hydroxyl value is 0.55-0.7mmol/g.
Polyether polyol: doxonothera D-2000D (functionality 2, molecular weight 2000), doxonothera EP330N (functionality 3, molecular weight 5000), available from Jiangxi Dongdao chemical Co., ltd.
The organosilicon diol is Shanghai Tyger tech-2120 or tech-2140.
End-capping agent A: the self-made coating is prepared by the following steps (1) to (2).
(1) Putting a calculated amount of dried bisphenol A type epoxy resin E44 into a reactor, adding a mixed solvent of n-butyl alcohol and ethylene glycol butyl ether, starting stirring until the epoxy resin is completely dissolved, and controlling the material temperature to be 85 ℃;
(2) Dropping calculated amounts of alpha-methacrylic acid (alpha-MAA), alpha- (methacryloyloxy) methyltriethoxysilane and benzoyl peroxide into a reactor, controlling a certain dropping reaction speed, continuously heating and stirring for reaction, controlling the temperature to be 90-95 ℃, reacting at constant temperature for 6-7 h, then vacuumizing, and distilling under reduced pressure for 0.5-1 h.
Wherein, bisphenol A type epoxy resin E44: MAA: α - (methacryloyloxy) methyltriethoxysilane =1 (molar ratio), the amount of the mixed solvent of n-butanol and butyl cellosolve is 10 to 15% of the total mass of the reaction, and benzaldehyde peroxide is 0.3 to 0.5% of the total mass of the reaction.
End-capping agent B: the self-made preparation method is the same as that of the end-capping reagent A, and the difference is that in the step (2), raw materials are Methyl Methacrylate (MMA) and gamma- (methacryloyloxy) propyl trimethoxy silane, and E44: MAA: γ - (methacryloyloxy) propyltrimethoxysilane = 1.
End-capping agent C: the self-made preparation method is the same as that of the end-capping reagent A, and the difference is that in the step (2), raw materials are hydroxyethyl methacrylate (HPMA) and gamma- (methacryloyloxy) propyl tri (beta-methoxyethoxy) silane, and E44: HPMA: γ - (methacryloyloxy) propyltris (β -methoxyethoxy) silane = 1.
Other raw materials which are not particularly described are all common commercial products.
Example 1
A single-component polyurethane waterproof coating comprises the following raw material components in parts by weight:
DL-2000D,65 parts by weight;
13 parts by weight of hydroxyl-terminated polybutadiene acrylonitrile;
EP330N,32 parts by weight;
tech-2120,6 parts by weight;
10 parts of dibutyl phthalate;
35 parts of nano calcium carbonate;
fumed silica, 9 parts by weight;
14 parts by weight of toluene diisocyanate;
12 parts of end-capping agent A;
0.8 part by weight of stannous octoate;
ethyl acetate, 6 parts by weight.
The preparation method of the single-component polyurethane waterproof coating comprises the following steps:
hydroxyl polybutadiene acrylonitrile, polyether polyol DL-2000D, EP330N, organosilicon diol tech-2120, plasticizer dibutyl phthalate, gradually added pigment, filler, nano calcium carbonate and gas phase silica are added into a strong dispersing machine, and the materials are uniformly dispersed;
transferring the dispersed slurry into a reaction kettle, stirring and heating to 100-110 ℃, and dehydrating for 2-3 hours under the relative vacuum degree of-0.08-0.1 MPa;
reducing the temperature to 70-80 ℃, adding a solvent ethyl acetate, then gradually adding toluene diisocyanate, stirring, then adding a catalyst stannous octoate with the formula amount of 1/4-1/2, heating to 75-85 ℃, and reacting for 3-4 hours; controlling the dripping speed of the toluene diisocyanate to be 1-2 parts by weight/s;
keeping the temperature at 75-85 ℃, adding an end-capping agent, and continuously stirring for reaction for 2-3 hours;
cooling to 50-60 ℃, adding the catalyst with the rest formula amount, and stirring for 0.5-1 hour;
cooling to below 50 deg.C, introducing nitrogen for protection, and discharging.
Example 2
The single-component polyurethane waterproof coating comprises the following raw material components in parts by weight:
the preparation process of the single-component polyurethane waterproof coating in this embodiment is substantially the same as that in embodiment 1, and details are not repeated here.
Example 3
A single-component polyurethane waterproof coating comprises the following raw material components in parts by weight:
DL-2000D,68 parts by weight;
12 parts by weight of hydroxyl-terminated polybutadiene acrylonitrile;
EP330N,30 parts by weight;
5 parts by weight of tech-2120;
10 parts of dibutyl phthalate;
35 parts of nano calcium carbonate;
fumed silica, 8 parts by weight;
14 parts by weight of toluene diisocyanate;
12 parts of end-capping agent C;
0.7 weight part of stannous octoate;
ethyl acetate, 7 parts by weight.
The preparation process of the single-component polyurethane waterproof coating in this embodiment is substantially the same as that in embodiment 1, and details are not repeated here.
Example 4
The single-component polyurethane waterproof coating comprises the following raw material components in parts by weight:
the preparation process of the single-component polyurethane waterproof coating in this embodiment is substantially the same as that in embodiment 1, and details are not repeated here.
Comparative example 1
A one-component polyurethane waterproofing paint, the composition and preparation process of which are similar to those of example 1, except that no blocking agent is added.
Comparative example 2
A one-component polyurethane waterproofing paint, the composition and preparation process of which are similar to those of example 1, except that the end-capping agent of example 1 is replaced with a conventional latent curing agent 3-hydroxyethyl-1, 3-oxazolidine.
The polyurethane waterproofing coatings prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to the performance test, and the test performances are shown in table 1.
TABLE 1
The test method comprises the following steps:
open time test
According to the test standard in GB/T19250-2013Performing test to obtain surface dry time t 1 。
Actual dry time test
Testing according to the test standard in GB/T19250-2013 to obtain the actual dry time T 2 。
Elongation at break test
The test was carried out according to the test standard in GB/T19250-2013.
Tensile Strength test
The test is carried out according to the test standard in GB/T19250-2013.
Tear Strength test
The test is carried out according to the test standard in GB/T19250-2013.
Adhesion Strength test
The test is carried out according to the test standard in GB/T19250-2013.
Water impermeability test
The test was carried out according to the test standard in GB/T19250-2013.
Measurement of Water-soaking adhesion
Test pieces are prepared according to the method specified in GB/T16777-2008.7.1 (method A), and the initial bonding strength of the test pieces is tested by curing for 7 days under standard test conditions (23 +/-2 ℃ C., relative humidity 50 +/-10%). The test piece was completely immersed in water, taken out at a predetermined time, and tested for adhesive strength after being left for 12 hours under standard test conditions, with a strength retention ratio = (adhesive strength/initial adhesive strength) × 100%.
As can be seen from the comparison between examples 1-4 and comparative examples 1-2, the coatings in examples 1-4 have better performances in various aspects such as bubble water adhesiveness, strength retention rate and the like; the adhesion properties and water-in-foam adhesion of the coatings of comparative examples 1 to 2 were significantly lower than those of examples 1 to 4.
Comparative example 1 the strength retention rate was most seriously decreased after soaking in water for 7 days, and the failure modes were interfacial failures, comparative example 2 the adhesive strength was gradually decreased with the increase of soaking time, and the failure modes were interfacial failures after soaking in water for 14 days. In examples 1 to 4, the silane modified end-capping agent was used, so that it was evident that the strength retention rate remained excellent after 30 days of water soaking, and the cohesive failure remained in the failure mode.
Therefore, the comparison shows that the silane modified end capping is used in the system, so that the adhesive force of the coating film to the cement base material can be greatly improved, particularly the adhesive strength retention rate of the coating film under the long-term water soaking condition is improved, the water absorption rate of the coating film is low and the swelling resistance is realized under the long-term water soaking condition, and the problems that the traditional single-group polyurethane waterproof coating is not firmly adhered to the cement base material and is not resistant to water soaking are solved.
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. At various points throughout this application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.
Claims (10)
1. A single-component polyurethane waterproof coating is characterized by comprising polyurethane film-forming resin, a filler and an additive;
the polyurethane film-forming resin comprises a molecular chain skeleton obtained by reacting hydroxyl-terminated polybutadiene acrylonitrile, organic silicon dihydric alcohol, polyether polyol and diisocyanate, and a blocking chain segment connected with the molecular chain skeleton;
the end-capping segment comprises a segment structure represented by formula 1,
in the formula 1, n is an integer of 1 to 25,
R 1 each occurrence is independently selected from hydrogen or a structure of formula 2 and at least one R 1 In order to have the structure shown in formula 2,
in the formula 2, R 2 、R 4 Each occurrence is independently selected from one of hydrogen or C1-C3 alkyl;
R 3 each occurrence is independently selected from hydrogen or C1-C8 alkyl or-R 3 'OH，R 3 ' is selected from C1-C8 alkylene;
R 5 selected from C1-C8 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from one of C1-C8 alkylene;
R 6 independently at each occurrence is selected from C1-C8 alkyl;
m is an integer of 1 to 3.
2. The one-component polyurethane waterproofing paint according to claim 1, wherein R in the formula 1 2 、R 4 Each occurrence is independently selected from hydrogen or CH 3 ，R 6 Independently at each occurrence, is selected from C1-C4 alkyl;
R 3 each occurrence is independently selected from hydrogen, C1-C4 alkyl or-R 3 One of' OH, R 3 ' is selected from C1-C4 alkylene;
R 5 independently at each occurrence, is selected from C1-C4 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from C1-C4 alkylene.
3. The one-component polyurethane waterproof coating material according to any one of claims 1 or 2, wherein the polyurethane film-forming resin is obtained by reacting a polyurethane prepolymer with a blocking agent;
the end-capping agent is bisphenol A epoxy resin,
Under the initiation of a free radical initiator, wherein the bisphenol A type epoxy resin: />
1-1;
the polyurethane prepolymer is obtained by reacting hydroxyl-terminated polybutadiene acrylonitrile, organic silicon diol, polyether polyol and diisocyanate.
4. The one-component polyurethane waterproofing coating according to claim 3, wherein said bisphenol A type epoxy resin comprises at least one of E54, E51, E44, E42, E21 or E20; and/or
The above-mentioned
Comprises one of methyl methacrylate, methacrylic acid, acrylic acid or hydroxyethyl methacrylate; and/or
The above-mentioned
Comprises one of gamma- (methacryloyloxy) propyl trimethoxy silane, alpha- (methacryloyloxy) methyl triethoxy silane, gamma- (methacryloyloxy) propyl tri (beta-methoxyethoxy) silane or N-methacryloyloxyethyl-N-dimethyl propyl trimethoxy silane hydrochloride.
5. The one-component polyurethane waterproof coating as claimed in claim 3, wherein the hydroxyl-terminated polybutadiene acrylonitrile has a number average molecular weight of 2500 to 3500 and a hydroxyl value of 0.55 to 0.7mmol/g; and/or
The polyether polyol is selected from one or more of polyether diol and polyether triol; and/or
The organic silicon double-end dihydric alcohol comprises a compound shown as a formula 3, the number average molecular weight of the organic silicon double-end dihydric alcohol is 1000-4000,
wherein R is 7 Is selected from C1-C25 alkyl, a is selected from an integer of 8-50; and/or
The diisocyanate is selected from one or more of aromatic diisocyanate or aliphatic diisocyanate.
6. The one-component polyurethane waterproof coating as claimed in claim 3, wherein the waterproof coating comprises the following raw material components in parts by weight:
100 parts of polyether polyol;
12-25 parts of hydroxyl-terminated polybutadiene acrylonitrile;
5-8 parts of organic silicon dihydric alcohol;
12-16 parts of diisocyanate;
12-18 parts of an end-capping reagent;
23-42 parts of a filler;
8-15 parts of additive.
7. The one-component polyurethane waterproofing coating according to claim 6,
the filler comprises one or more of carbon black, titanium dioxide, kaolin, fumed silica, heavy calcium, barium sulfate, silica micropowder and talcum powder; and/or the presence of a gas in the gas,
the additive comprises a plasticizer, and the plasticizer comprises one or more of dioctyl phthalate, dibutyl phthalate, diisononyl phthalate, trioctyl phosphate, citric acid ester and chlorinated paraffin.
8. A preparation method of a single-component polyurethane waterproof coating is characterized by comprising the following steps:
reacting 100 parts by weight of polyether polyol, 12-25 parts by weight of hydroxyl-terminated polybutadiene acrylonitrile, 5-8 parts by weight of organic silicon diol, 12-16 parts by weight of diisocyanate, a filler and an additive in an organic solvent in the presence of a catalytic amount of a catalyst for a urethanization reaction to obtain a first slurry;
reacting the first slurry with 12-18 parts by weight of end-capping reagent in the presence of a catalytic amount of catalyst for a urethanization reaction to obtain a single-component polyurethane waterproof coating, wherein the end-capping reagent has a structure shown in a formula 4,
in the formula 4, n is an integer of 1 to 25,
R 1 each occurrence is independently selected from hydrogen or a structure of formula 2 and at least one R 1 In order to have the structure shown in the formula 2,
in the formula 2, R 2 、R 4 Each occurrence is independently selected from one of hydrogen or C1-C3 alkyl;
R 3 each occurrence is independently selected from hydrogen or C1-C8 alkyl or-R 3 'OH，R 3 ' is selected from C1-C8 alkylene;
R 5 selected from C1-C8 alkylene or
One of (1), R 5 ' and R 5 "is independently selected from one of C1-C8 alkylene;
R 6 independently at each occurrence, is selected from C1-C8 alkyl;
m is an integer of 1 to 3.
9. The method for preparing the one-component polyurethane waterproof coating material according to claim 8, wherein the catalyst is one or more selected from dibutyltin dilaurate, stannous octoate and lead isooctanoate.
10. The method for preparing the one-component polyurethane waterproof coating material according to claim 8, wherein the method comprises:
the blocking agent is prepared by:
dissolving bisphenol A epoxy resin in a solvent to obtain an epoxy resin solution;
mixing the epoxy resin solution with
And a free radical initiator, reacting at the initiation temperature of the free radical initiator to obtain the capping agent,
wherein, the bisphenol A type epoxy resin,
The molar ratio of 1. />
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