CN112898889B - Polyurethane waterproof coating and application thereof - Google Patents
Polyurethane waterproof coating and application thereof Download PDFInfo
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- CN112898889B CN112898889B CN202110104253.3A CN202110104253A CN112898889B CN 112898889 B CN112898889 B CN 112898889B CN 202110104253 A CN202110104253 A CN 202110104253A CN 112898889 B CN112898889 B CN 112898889B
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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
- C09D175/08—Polyurethanes from polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a polyurethane waterproof coating and application thereof, wherein the polyurethane waterproof coating comprises a polyurethane prepolymer and an auxiliary agent, the raw materials of the polyurethane prepolymer comprise polyol, isocyanate and a secondary amine compound, and the secondary amine compound is one or more of compounds shown in a formula (I):
wherein R is1Is a branched alkylene group; r2Is H or C1‑10Alkyl or is selected from C1‑6Alkyl radical, C1‑6C substituted by one or more of alkoxy1‑10Alkyl or phenyl; the polyurethane prepolymer is prepared by mixing polyol, secondary amine compound and partial isocyanate for reaction, and then adding the rest isocyanate for reaction again; the waterproof coating is suitable for machine spraying on a high-temperature base layer, can give consideration to both sag resistance and viscosity balance, and is particularly suitable for spraying construction on the base layer with the temperature of more than 50 ℃.
Description
Technical Field
The invention belongs to the field of building waterproofing, and particularly relates to waterproof construction with high temperature and a vertical face or a slope face for a building construction base layer, in particular to a polyurethane waterproof coating and application thereof.
Background
At present, the conventional polyurethane coating is a solvent-containing non-environment-friendly coating, and the solvent is volatilized during construction, so that the conventional polyurethane coating has a large taste and causes air pollution. Because the viscosity of the polyurethane prepolymer is high, a manufacturer must add a filler to reduce the cost, so that the viscosity of the coating is high, and the coating is difficult to construct and apply without adding a solvent. Meanwhile, in some domestic large-scale projects, such as basement wall surfaces of large-scale system stadiums, high-speed rails, subways, tunnels, civil air defense and the like, waterproof construction needs to be carried out on vertical surfaces or slope surfaces. Because of the elevation or slope, the construction is inconvenient and the quality problem is easy to occur. The waterproof paint can form a seamless waterproof layer, but the universal paint can flow when being coated on a vertical surface or a slope surface, so that the upper part is thin and the lower part is thick. The upper part of the coating film is not hung up to a certain thickness, and the surface of the coating film is uneven in thickness, so that the coating film with the thickness of 1.5mm can be coated four or five times. In addition, the temperature in most areas in summer is generally higher in China, the temperature of a base layer on site can reach more than 50 ℃ after being exposed to the sun, and at the moment, the sagging resistant polyurethane is easy to flow after construction of a construction vertical face of common sagging resistant polyurethane.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, and to provide a polyurethane waterproof coating material which is suitable for machine spraying on a high-temperature substrate and has both sag resistance and viscosity balance.
The invention also provides the application of the polyurethane waterproof coating in spraying construction on a base layer with the temperature of more than 50 ℃, and the polyurethane waterproof coating has excellent anti-sagging performance when being constructed on the high-temperature base layer, particularly on the high-temperature base layer of a vertical face or a slope face.
In order to solve the technical problems, the invention adopts a technical scheme as follows:
the polyurethane waterproof coating comprises a polyurethane prepolymer and an auxiliary agent, wherein the polyurethane prepolymer comprises polyol, isocyanate and a secondary amine compound, and the secondary amine compound is one or a combination of more of compounds shown in a formula (I):
wherein R is1Is a branched alkylene group;
R2is H or C1-10Alkyl or is selected from C1-6Alkyl radical, C1-6C substituted by one or more of alkoxy1-10Alkyl or phenyl;
the polyurethane prepolymer is prepared by mixing and reacting polyol, secondary amine compound and partial isocyanate, and then adding the rest isocyanate for reacting again.
According to some preferred aspects of the invention, R1Is C3-10Branched alkylene radical, R1Can be-C (CH)3)2-、-C(CH2CH3)2-、-C(CH2CH2CH3)2-、-CH(CH3)-、-CH(CH2CH3)-、-C{CH(CH3)2}2-、-C{CH(CH2CH3)2}2-、-C{CH2CH(CH3)2}2-、-C{CH2CH2CH(CH3)2}2-and so on.
According to some preferred aspects of the invention, R2Is H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxyisopropyl, methoxybutyl, methoxyisobutyl, methoxypentyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxyisopropyl, ethoxybutyl, ethoxyisobutyl, ethoxypentyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl or phenyl.
According to some preferred and specific aspects of the present invention, the secondary amine compound is a combination of one or more selected from the group consisting of compounds represented by the following structures:
according to some preferred aspects of the present invention, the mass ratio of the polyol, the isocyanate and the compound of formula (I) is 1: 0.2-0.5: 0.05-0.15.
According to some preferred aspects of the present invention, the polyol is composed of a diol and a triol, and the feed mass ratio of the diol to the triol is 1: 0.1-1. For example, polyether 330N, polyether 4000, polyether 2000, polyether 3050, polyether 1000 and polyether 400, which are manufactured by Shandong Daihao chemical industry Co., Ltd.
According to some preferred aspects of the present invention, the isocyanate is a combination of at least two selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate. For example, at least two selected from the group consisting of diphenylmethane diisocyanate available from Pasteur, Germany under the trade designation MDI-MI, MDI50, MDI100, IPDI, HDI, modified MDI103C, and TDI-80, available from Bayer, Germany under the trade designation TDI-80.
According to some preferred aspects of the present invention, the mixing reaction temperature of the polyol, the secondary amine compound and the partial isocyanate in the preparation of the polyurethane prepolymer is 60 ℃ or less.
According to some preferred aspects of the present invention, the reaction temperature after the addition of the remaining isocyanate during the preparation of the polyurethane prepolymer is 75 to 85 ℃.
In the invention, the control of the temperature in the synthesis process of the polyurethane prepolymer is beneficial to controlling the reaction degree to form an expected molecular structure, ensuring the balance of sag resistance and viscosity at high temperature and simultaneously being beneficial to spraying construction.
According to some preferred aspects of the invention, the adjuvant comprises a catalyst consisting of dibutyltin dilaurate, pentamethyldipropylenetriamine and zinc isooctoate in a mass feed ratio of 1: 0.4-0.8: 0.2-0.6.
According to some specific and preferred aspects of the present invention, the auxiliaries further include fillers, plasticizers, dispersants, reactive diluents, solvents, thixotropic agents, water scavengers and defoamers; the polyurethane waterproof coating comprises, by mass, 20-50 parts of a polyurethane prepolymer, 20-50 parts of a filler, 5-30 parts of a plasticizer, 0.1-1 part of a dispersant, 0.3-2 parts of an active diluent, 0.5-15 parts of a solvent, 0.1-2 parts of a thixotropic agent, 0.1-1 part of a water removing agent, 0.05-1 part of a catalyst and 0.1-1 part of a defoaming agent.
According to some particular aspects of the invention, the filler comprises heavy and/or nano-sized fillers. The heavy filler is one or more of titanium dioxide, heavy calcium carbonate, kaolin and talcum powder. The nano-scale filler is one or more of gypsum whisker, fumed silica, nano calcium carbonate, nano aluminum nitride, nano boron nitride and nano aluminum borate.
According to some specific aspects of the invention, the antifoaming agent comprises a physical antifoaming agent and/or a chemical antifoaming agent. The physical defoaming agent is selected from polysiloxane defoaming agent and/or silicone defoaming agent, and the chemical defoaming agent is one or more of calcium oxide, magnesium oxide, calcium hydroxide and latent curing agent. The defoamer may be a 066N defoamer manufactured by bike chemical, a courteous 5500, an organosilicon defoamer of shanghai tag.
According to some specific aspects of the present invention, the plasticizer includes, but is not limited to, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), chlorinated paraffin, dioctyl adipate, glycol benzoate, trioctyl phosphate, phenyl alkylsulfonate. For example, it may be one or more selected from DINP (Chinese name: diisononyl phthalate) produced by Taiwan Union, DIDP, chlorinated paraffin produced by Danyang auxiliary agent factory, vegetable oil and fat of Ight, dioctyl adipate, glycol benzoate, trioctyl phosphate, and phenyl alkylsulfonate.
According to some specific aspects of the present invention, the dispersant is a combination of one or more selected from titanate-based dispersants, silane-based dispersants, and carboxylic-based dispersants. For example, the dispersant may be silane coupling agent WD50 from martial silica company, f108 jonzhou's temporary assistant, KH550, KH560, courtesy chemical 9250 dispersant, and the like.
According to some specific aspects of the invention, the reactive diluent is zoldine RD20 reactive diluent from Angus corporation.
According to some specific aspects of the invention, the solvent is mineral spirits No. 230.
According to some particular aspects of the invention, the thixotropic agent is fumed silica, polymeric resin wax powder, lact of arkema.
According to some specific aspects of the invention, the water scavenger is a molecular sieve and/or isocyanate water scavenger. For example, the p-toluenesulfonyl isocyanate micro-molecular water removal agent and the Luoyangjianlong micro-nano molecular sieve can be used in Pasf, Germany.
The invention provides another technical scheme that: the polyurethane waterproof coating is applied to spraying construction on a base layer with the temperature of more than 50 ℃, and the base layer is obliquely arranged and/or vertically arranged.
According to the invention, the compound of formula (I) in the invention is prepared by aminomethylation reaction of phenol containing active alpha-H, aldehyde compound and compound of primary amine with double ends, wherein the compound of primary amine with double ends preferably contains branched alkylidene; the aldehyde compounds are common aldehydes including, but not limited to, formaldehyde, acetaldehyde, benzaldehyde, and the like. Preferably, the process for preparing the compound of formula (I) according to the present invention comprises the steps of:
(a) heating phenol and aldehyde compound to react;
(b) adding a compound (H) of a double-ended primary amine to be reacted to the reaction solution after the reaction of step (a)2N-R1-NH2) Mixing, heating for reaction, then vacuum dehydrating and/or heating for dehydrating, controlling the water content below 500ppm until obtaining a transparent viscous liquid product, and preparing the compound shown in the formula (I).
Preferably phenol, aldehyde compounds and compounds of primary amine at both ends (H)2N-R1-NH2) The feeding mol ratio of the raw materials is 1: 0.5-2: 0.5-1.
Preferably, the reaction temperature of the phenol with the aldehyde compound in step (a) is 50 to 80 ℃.
Preferably, in step (a), the reaction of the phenol with the aldehyde compound is carried out in the presence of an alkaline earth metal magnesium-type catalyst. The alkaline earth metal magnesium type catalyst is composed of magnesium hydroxide and magnesium oxide with the feeding molar ratio of 1: 0.8-1.2.
Preferably, in step (b), a compound (H) having a primary amine at both ends is added2N-R1-NH2) The reaction temperature thereafter was 100-150 ℃.
The invention provides another technical scheme that: a preparation method of the polyurethane waterproof coating comprises the following steps:
(1) preparation of polyurethane prepolymer
Mixing a polyol with the specific secondary amine compound, adding part of isocyanate, and carrying out a first-stage reaction at a temperature of below 60 ℃; then adding the rest isocyanate, heating to 75-85 ℃, and carrying out second-stage reaction to prepare a polyurethane prepolymer; wherein, the first stage reaction and the second stage reaction are respectively carried out under the protection of protective gas;
(2) and (2) mixing the polyurethane prepolymer prepared in the step (1) with an auxiliary agent to prepare the polyurethane waterproof coating.
In the invention, the isocyanate is added in batches mainly for ensuring that the crosslinking density of the early molecular weight production structure is large enough to form polyurea graft and provide necessary molecular structure conditions for the thixotropy of a system.
According to some preferred aspects of the present invention, in the step (1), the polyol and the secondary amine compound are subjected to a vacuum dehydration operation before the first-stage reaction is performed, and the moisture content is controlled to be less than 0.05%.
According to some preferred aspects of the present invention, in the step (1), since the first-stage reaction is an exothermic reaction, the first-stage reaction is controlled to be stopped after the reaction temperature no longer rises and the temperature stabilizes.
According to some preferred aspects of the present invention, in the step (1), the protective gas may be nitrogen, argon, or the like.
According to some preferred aspects of the present invention, in the step (1), the NCO content of the polyurethane prepolymer is controlled to 2 to 6% by mass.
According to some preferred aspects of the present invention, in step (1), a portion of the isocyanate added in the first stage reaction is 0.2 to 0.5, preferably 0.20 to 0.40, based on the total isocyanate.
According to some preferred aspects of the present invention, in the step (2), the auxiliaries further include a filler, a plasticizer, a dispersant, a reactive diluent, a solvent, a thixotropic agent, a catalyst, a water scavenger, and an antifoaming agent; wherein the filler and the plasticizer are dehydrated before being added.
According to some preferred aspects of the present invention, in the step (2), the plasticizer and the filler are added after the remaining auxiliaries in the auxiliaries.
According to some preferred aspects of the present invention, in the step (2), after the polyurethane prepolymer prepared in the step (1) is mixed with the auxiliary agent, a vacuum defoaming treatment is further performed, wherein the vacuum defoaming treatment is performed at a vacuum degree of-0.09 to 0.1 MPa.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
the polyurethane waterproof coating is prepared by innovatively adopting the specific secondary amine compound, the polyurethane prepolymer prepared by the secondary amine compound has an ideal molecular structure, and can have better thixotropic property (the specific secondary amine compound has larger steric hindrance effect on one hand, so that the reaction is mild, the formed molecular structure is regular and compact, on the other hand, the structure is symmetrical, the molecular structure is more stretched, the function of a hydrogen bond can be fully utilized, more thixotropic contact points are provided, better thixotropy is provided for a system), the excellent anti-sagging property and the proper viscosity of the waterproof coating can be endowed, especially for a high-temperature base layer, the special structure of the waterproof coating can still realize the anti-sagging property and the viscosity on the high-temperature base layer, and thus the polyurethane waterproof coating can be sprayed and constructed by a machine, especially, the spraying construction is carried out on a vertical surface or a slope surface, and the defect that the waterproof coating is difficult to spray due to the fact that the temperature of a base layer is too high caused by external factors such as summer and the like is overcome.
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
In the following examples, all starting materials are either commercially available or prepared by conventional methods in the art, unless otherwise specified.
Example 1
This example provides a secondary amine compound having the structure shown in formula (I-1):
the preparation method comprises the following steps:
(a) mixing phenol (1mol), formaldehyde aqueous solution (containing 2mol of formaldehyde) with the mass fraction of 37 percent and 0.05mol of alkaline earth metal magnesium type catalyst (composed of magnesium hydroxide and magnesium oxide with the feeding molar ratio of 1: 1), heating to 60 ℃, and reacting for 1 hour;
(b) adding the isopropylenediamine (H) to be reacted into the reaction solution after the reaction in the step (a)2N-C(CH3)2-NH20.5mol), mixing, heating to 120 ℃, reacting for 4 hours, then dehydrating in vacuum, controlling the water content to be below 500ppm until a transparent viscous liquid product is obtained, and preparing the compound shown in the formula (I-1).
Example 2
This example provides a secondary amine compound having the structure shown in formula (I-2):
the preparation method comprises the following steps:
(a) mixing phenol (1mol), formaldehyde aqueous solution (containing 2mol of formaldehyde) with the mass fraction of 37 percent and 0.05mol of alkaline earth metal magnesium type catalyst (composed of magnesium hydroxide and magnesium oxide with the feeding molar ratio of 1: 1), heating to 60 ℃, and reacting for 1 hour;
(b) adding 3-diaminopentane (H) to be reacted to the reaction solution after the reaction in step (a)2N-C(CH2CH3)2-NH20.5mol), mixing, heating to 120 ℃, reacting for 4 hours, then dehydrating in vacuum, controlling the water content to be below 500ppm until a transparent viscous liquid product is obtained, and preparing the compound shown in the formula (I-2).
Example 3
This example provides a secondary amine compound having the structure shown in formula (I-5):
the preparation method comprises the following steps:
(a) mixing phenol (1mol), benzaldehyde (2mol) and 0.05mol of alkaline earth metal magnesium type catalyst (composed of magnesium hydroxide and magnesium oxide with the feeding molar ratio of 1: 1), heating to 80 ℃, and reacting for 1 h;
(b) adding the isopropylenediamine (H) to be reacted into the reaction solution after the reaction in the step (a)2N-C(CH3)2-NH20.5mol), mixing, heating to 120 ℃, reacting for 4 hours, then dehydrating in vacuum, controlling the water content to be below 500ppm until a transparent viscous liquid product is obtained, and preparing the compound shown in the formula (I-5).
Example 4
The embodiment provides a polyurethane waterproof coating, which comprises the following raw materials: 420kg of polyurethane prepolymer, 250kg of filler, 100kg of plasticizer, 1kg of dispersant, 20kg of reactive diluent, 100kg of solvent, 5kg of thixotropic agent, 1kg of water removing agent, 1kg of catalyst and 3kg of defoaming agent.
The polyurethane prepolymer comprises the following raw materials: 150kg of Dongda polyether triol 330N, 150kg of Dongda polyether diol 2000, 20kg of the secondary amine compound of example 1, 50kg of Basff MDI-MI and 50kg of Basff modified MDI103 c.
The filler consists of 150kg Suzhou lida ultramicro LD600 and 100kg Hunan Jinjian B-type nanometer powder;
the plasticizer is 100kg of DINP produced by Taiwan;
the dispersant is 1kg of silane coupling agent WD50 of Hubei Wuda organosilicon company;
the reactive diluent was 20kg zoldine RD20 reactive diluent from Angus, USA;
the solvent is 100kg No. 230 solvent oil;
the thixotropic agent is 5kg of Deshan PM20L aerosil;
the water removal agent is 1kg of p-toluenesulfonyl isocyanate micromolecule water removal agent of German Pasf;
the catalyst consists of 0.5kg of dibutyltin dilaurate of Beijing Akema, 0.3kg of pentamethyl dipropylene triamine of American air chemical industry and 0.2kg of zinc isooctanoate of American advanced chemical;
the defoaming agent consists of 0.5kg of magnesium oxide in Wuzehui chemical industry, 0.5kg of calcium oxide in Jiangsu Xin and 2kg of defoaming agent in Bike chemical 066N.
The preparation method of the polyurethane waterproof coating comprises the following steps:
(1) preparing a polyurethane prepolymer:
150kg of Dongda polyether triol 330N, 150kg of Dongda polyether diol 2000 and 20kg of the secondary amine compound of example 1 were mixed, slowly heated to 120 ℃ under stirring, and vacuum dehydrated for 2 hours until the moisture content was less than 0.05%;
reducing the temperature to be below 60 ℃, adding 10kg of Basf MDI-MI and 10kg of Basf modified MDI103c, carrying out the first-stage reaction under the condition that the temperature is below 60 ℃, adding 40kg of Basf MDI-MI and 40kg of Basf modified MDI103c after the reaction temperature is not increased and stable any more, heating to 80 +/-2 ℃, carrying out the second-stage reaction under the condition of heat preservation until the mass content of NCO is 3.8%, and stopping the reaction to prepare a polyurethane prepolymer; wherein, the first stage reaction and the second stage reaction are respectively carried out under the protection of nitrogen;
(2) mixing the polyurethane prepolymer prepared according to the step (1) with 5kg of Deshan PM20L gas silicon, 0.5kg of magnesium oxide in Wuze-Zi chemical industry and 0.5kg of calcium oxide in Jiangsu-Tuxin, 100kg of No. 230 solvent oil, 20kg of Zoldine RD20 reactive diluent of American angus company, 2kg of defoamer in Pick chemical industry 066N, 1kg of silane coupling agent WD50 of Hubei Wu-Dai silicone company, 0.5kg of dibutyltin dilaurate of Beijing Akma, 0.3kg of pentamethyl dipropylene triamine in American air chemical industry, 0.2kg of American lead chemical zinc isooctanoate, 0.5kg of small molecule water remover for toluene sulfonyl isocyanate of Germany Basbauv, then adding 100kg of dehydrated DINP produced by the union of Chinese Taiwan, 150kg of Sulida ultramicro LD600, 100kg of German Nanjin B nano calcium carbonate, mixing, and defoaming after 0.04 +/-0.02 MPa, and testing the fineness to 50 mu m by a scraper fineness tester to prepare the polyurethane waterproof coating.
The properties were measured as follows: viscosity of 11200mpa.s (25 ℃), 5800mpa.s (50 ℃), solid content of 88.9%, surface drying time of 2 hours, actual drying time of 6 hours, 7-day tensile strength of 4.2MPa, elongation at break of 874%, and tear strength of 23N/mm;
after the mechanical spraying construction of the base surface at 50 ℃, the conditions are as follows: the coating thickness is 1.5mm at a time without flowing.
Example 5
Basically, the method is the same as the method in example 4, and only differs from the method in that: the secondary amine compound was replaced with 22kg of the compound prepared in example 2. The properties were measured as follows: viscosity 12100mpa.s (25 ℃), 6100mpa.s (50 ℃), solid content 88.8%, surface drying time 2 hours, actual drying time 5 hours, 7 days tensile strength 3.9MPa, elongation at break 976%, tear strength 22N/mm;
after the mechanical spraying construction of the base surface at 50 ℃, the conditions are as follows: the coating thickness is 1.5mm at a time without flowing.
Example 6
Basically, the method is the same as the method in example 4, and only differs from the method in that: the secondary amine compound was replaced with 30.8kg of the compound prepared in example 3.
The properties were measured as follows: viscosity of 13200mpa.s (25 ℃), 7100mpa.s (50 ℃), solid content of 89%, surface drying time of 2 hours, actual drying time of 7 hours, 7 days tensile strength of 3.8MPa, elongation at break of 750%, and tear strength of 16N/mm;
after the mechanical spraying construction of the base surface at 50 ℃, the conditions are as follows: the coating thickness is 1.5mm at a time without flowing.
Example 7
Basically, the method is the same as the method in example 4, and only differs from the method in that: in the preparation of the polyurethane prepolymer, 15kg of BASF MDI-MI and 15kg of BASF modified MDI103c were added for the first stage reaction, and then 35kg of BASF MDI-MI and 35kg of BASF modified MDI103c were added for the second stage reaction.
The properties were measured as follows: viscosity of 22000mpa.s (25 ℃), 12100mpa.s (50 ℃), solid content of 88.9%, surface drying time of 2 hours, actual drying time of 6 hours, 7 days tensile strength of 3.1MPa, elongation at break 678%, and tear strength of 18N/mm;
after the mechanical spraying construction of the base surface at 50 ℃, the conditions are as follows: the coating thickness is 1.5mm at a time without flowing.
Comparative example 1
Basically, the method is the same as the method in example 4, and only differs from the method in that: the secondary amine compound of example 1 was replaced with the commercially available commonly used chain extender clearlink 10004, 4' bis sec-butylaminodicyclohexylmethane.
The properties were measured as follows: viscosity of 35000mpa.s (25 ℃), 21900mpa.s (50 ℃), solid content of 88.8%, surface drying time of 2 hours, actual drying time of 6 hours, 7-day tensile strength of 1.1MPa, elongation at break of 546%, and tear strength of 15N/mm; after the mechanical spraying construction of the base surface at 50 ℃, the conditions are as follows: the coating thickness is 1mm at a time.
Comparative example 2
Basically, the method is the same as the method in example 4, and only differs from the method in that: the secondary amine compound of example 1 was replaced with methylene bis ortho chloroaniline (moca), a commercially commonly used chain extender.
The properties were measured as follows: the viscosity is 45370mpa.s (25 ℃), 28900mpa.s (50 ℃), the solid content is 88.9%, the surface drying time is 2 hours, the actual drying time is 6 hours, the 7-day tensile strength is 1.8MPa, the elongation at break is 457%, and the tear strength is 13N/mm;
after the mechanical spraying construction of the base surface at 50 ℃, the conditions are as follows: the coating thickness is 1mm at a time.
Comparative example 3
Basically, the method is the same as the method in example 4, and only differs from the method in that: the polyurethane prepolymer was prepared by mixing the polyol, the secondary amine compound of example 1, and all the isocyanates and reacting them together at 80. + -. 2 ℃.
The properties were measured as follows: viscosity of 34600mpa.s (25 ℃), 17600mpa.s (50 ℃), solid content of 89%, surface drying time of 2 hours, actual drying time of 6 hours, 7-day tensile strength of 2.3MPa, elongation at break of 478%, and tear strength of 15N/mm;
after the mechanical spraying construction of the base surface at 50 ℃, the conditions are as follows: the coating thickness is 1mm at a time.
Comparative example 4
Basically, the method is the same as the method in example 4, and only differs from the method in that: the polyurethane prepolymer was prepared by reacting a polyol with all isocyanates at 80 ± 2 ℃ for 2 hours, and then reacting with the secondary amine compound of example 1 for 1 hour.
The properties were measured as follows: viscosity of 44900mpa.s (25 ℃), 22300mpa.s (50 ℃), solid content of 89%, surface drying time of 2 hours, actual drying time of 6 hours, 7-day tensile strength of 2.1MPa, elongation at break of 786%, and tear strength of 16N/mm;
after the mechanical spraying construction of the base surface at 50 ℃, the conditions are as follows: the coating thickness is 1mm at a time.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (7)
1. The polyurethane waterproof coating is characterized by comprising the following raw materials in parts by mass: 20-50 parts of polyurethane prepolymer, 20-50 parts of filler, 5-30 parts of plasticizer, 0.1-1 part of dispersant, 0.3-2 parts of active diluent, 0.5-15 parts of solvent, 0.1-2 parts of thixotropic agent, 0.1-1 part of water removing agent, 0.05-1 part of catalyst and 0.1-1 part of defoaming agent;
the raw materials of the polyurethane prepolymer comprise polyol, isocyanate and a secondary amine compound, wherein the secondary amine compound is one or more of compounds shown in a formula (I):
wherein R is1Is a branched alkylene group;
R2is H, methyl, ethyl, propyl, butyl, pentyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl or phenyl;
the polyurethane prepolymer is prepared by mixing and reacting polyol, a secondary amine compound and part of isocyanate, and then adding the rest isocyanate for reacting again;
the catalyst is composed of dibutyltin dilaurate, pentamethyl dipropylene triamine and zinc isooctanoate, wherein the mass ratio of the materials is 1: 0.4-0.8: 0.2-0.6.
2. The polyurethane waterproofing coating according to claim 1, wherein R is R1Is C3-10A branched alkylene group.
3. The polyurethane waterproof coating material according to claim 1, wherein the secondary amine compound is one or more selected from the group consisting of compounds represented by the following structures:
4. the polyurethane waterproof coating material as claimed in claim 1, wherein the mass ratio of the polyol to the isocyanate to the compound represented by the formula (i) is 1: 0.2-0.5: 0.05-0.15; and/or the NCO content of the polyurethane prepolymer is 2-6% by mass.
5. The polyurethane waterproof coating material according to claim 1, wherein the polyol is composed of a diol and a triol, and the mass ratio of the diol to the triol is 1: 0.1-1; and/or the isocyanate is a combination of at least two selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.
6. The polyurethane waterproof coating as claimed in claim 1, wherein the temperature of the mixing reaction of the polyol, the secondary amine compound and the partial isocyanate in the preparation of the polyurethane prepolymer is not more than 60 ℃, and the reaction temperature after the addition of the remaining isocyanate is 75-85 ℃.
7. Use of the polyurethane waterproofing paint according to any one of claims 1 to 6 for spray application on a substrate having a temperature of 50 ℃ or higher, the substrate being disposed in an inclined or vertical manner.
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| PCT/CN2021/102729 WO2022160584A1 (en) | 2021-01-26 | 2021-06-28 | Polyurethane waterproof coating, preparation method therefor and use thereof |
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| CN117363086A (en) * | 2021-08-06 | 2024-01-09 | 江苏凯伦建材股份有限公司 | Application of polyamide wax composition in preparation of polyurethane waterproof coating |
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