WO2022160584A1 - Polyurethane waterproof coating, preparation method therefor and use thereof - Google Patents

Polyurethane waterproof coating, preparation method therefor and use thereof Download PDF

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Publication number
WO2022160584A1
WO2022160584A1 PCT/CN2021/102729 CN2021102729W WO2022160584A1 WO 2022160584 A1 WO2022160584 A1 WO 2022160584A1 CN 2021102729 W CN2021102729 W CN 2021102729W WO 2022160584 A1 WO2022160584 A1 WO 2022160584A1
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Prior art keywords
waterproof coating
polyurethane
isocyanate
polyurethane waterproof
reaction
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PCT/CN2021/102729
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French (fr)
Chinese (zh)
Inventor
贺小钢
李忠人
周围
单永胜
马世界
王仁杰
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江苏凯伦建材股份有限公司
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Publication of WO2022160584A1 publication Critical patent/WO2022160584A1/en

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Classifications

    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention belongs to the field of building waterproofing, particularly relates to waterproofing construction for building base layers with high temperature and façades or slopes, in particular to a polyurethane waterproof coating and application thereof.
  • conventional polyurethane coatings are basically non-environmentally friendly coatings containing solvents.
  • the solvents in the coatings are volatile, which makes the environment smell bad and causes air pollution.
  • the viscosity of the polyurethane prepolymer itself is high, and the manufacturer must add fillers in order to reduce the cost, resulting in a further increase in the viscosity of the coating. If no solvent is added, it will be difficult to apply.
  • some large-scale projects in China such as the South-to-North Water Transfer Project, basement walls of large venues, high-speed railways, subways, tunnels, civil air defense, etc., need to be waterproofed on the facade or slope, which makes the construction inconvenient.
  • a seamless waterproof layer can be formed with a waterproofing paint, but the general purpose paint will run off when applied to a facade or slope, resulting in a thin upper part and a thick lower part. The thickness of the upper part cannot be hung, and the thickness of the coating film surface is uneven. If you want to apply a 1.5mm thick coating film, you may need to apply it four or five times. In addition, the temperature in most areas of the country in summer is generally high, and the grassroots on site can even reach above 50 °C after exposure to the sun. At this time, ordinary anti-sag polyurethane coatings are prone to flow after the facade is applied, and it needs to be repeatedly painted manually. And it takes a long time to reach the required thickness after each brushing, which is not only time-consuming and labor-intensive, but also a great waste of paint.
  • 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 suitable for spraying on high-temperature base layers and taking into account sag resistance and viscosity balance, especially suitable for machinery. Spraying, basically one spraying can meet the requirements.
  • the present invention also provides a preparation method of the above-mentioned polyurethane waterproof coating.
  • the present invention also provides the use of the above-mentioned polyurethane waterproof coating for spraying construction on the base layer with a temperature of over 50°C, and the construction on the high-temperature base layer, especially on the high-temperature base layer on the facade or slope surface, also has excellent sag resistance.
  • a polyurethane waterproof coating comprises a polyurethane prepolymer and an auxiliary, the raw materials of the polyurethane prepolymer include polyol, isocyanate and secondary amine compound, and the secondary amine compound is selected from formula (I) Combinations of one or more of the compounds shown:
  • R 1 is branched alkylene
  • R 2 is H or C 1-10 alkyl, or C 1-10 alkyl or phenyl substituted by one or more selected from C 1-6 alkyl, C 1-6 alkoxy;
  • the polyurethane prepolymer is prepared by mixing and reacting polyol, secondary amine compound and part of isocyanate, and then adding the remaining isocyanate to react again.
  • R 1 is C 3-10 branched chain alkylene, and R 1 can be -C(CH 3 ) 2 -, -C(CH 2 CH 3 ) 2 -, -C(CH 2 CH 2 CH 3 ) 2 -, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C ⁇ CH(CH 3 ) 2 ⁇ 2 -, -C ⁇ CH(CH 2 CH 3 ) 2 ⁇ 2 -, -C ⁇ CH 2 CH(CH 3 ) 2 ⁇ 2 -, -C ⁇ CH 2 CH(CH 3 ) 2 ⁇ 2 - and so on.
  • R 2 is H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, methoxymethyl, methoxyethyl, methoxy methoxypropyl, methoxyisopropyl, methoxybutyl, methoxyisobutyl, methoxypentyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxy isopropyl, ethoxybutyl, ethoxyisobutyl, ethoxypentyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl or phenyl.
  • the secondary amine compound is a combination of one or more selected from the compounds represented by the following formula:
  • the mass ratio of the polyol, the isocyanate and the compound represented by the formula (I) is 1:0.2-0.5:0.05-0.15.
  • 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.
  • it can be polyether 330N, polyether 4000, polyether 2000, polyether 3050, polyether 1000, and polyether 400 produced by Shandong Dongda Chemical Industry Co., Ltd.
  • the isocyanate is a polyisocyanate.
  • the polyisocyanate is selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate A combination of at least two of isocyanate and hexamethylene diisocyanate.
  • it can be selected from the MDI-MI diphenylmethane diisocyanate produced by BASF in Germany, MDI50 of Wanhua Chemical, MDI100 of Wanhua Chemical, IPDI of Wanhua Chemical, HDI of Wanhua Chemical, BASF's Modified MDI 103C, at least two of the toluene diisocyanates with the brand name of TDI-80 from Bayer, Germany.
  • the temperature of the mixing reaction of the polyol, the secondary amine compound and the partial isocyanate is less than or equal to 60°C.
  • the reaction temperature after adding the remaining isocyanate is 75-85°C.
  • the temperature control during the synthesis of the polyurethane prepolymer is beneficial to control the degree of reaction to form the expected molecular structure, to ensure the balance between sag resistance and viscosity at high temperature, and at the same time, it is beneficial to spray construction.
  • the auxiliary agent comprises a catalyst
  • the catalyst is composed of dibutyltin dilaurate, pentamethyldipropylenetriamine and isopropylamine with a mass ratio of 1:0.4-0.8:0.2-0.6.
  • Zinc octoate composition is composed of dibutyltin dilaurate, pentamethyldipropylenetriamine and isopropylamine with a mass ratio of 1:0.4-0.8:0.2-0.6.
  • the adjuvant further includes filler, plasticizer, dispersant, reactive diluent, solvent, thixotropic agent, dewatering agent and defoaming agent; in parts by mass, In the polyurethane waterproof coating, 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 reactive diluent, and 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 defoamer.
  • the fillers include heavy fillers and/or nanoscale fillers.
  • the heavy filler is one or more combinations selected from titanium dioxide, heavy calcium carbonate, kaolin, and talc.
  • the nano-scale filler is a combination of one or more selected from gypsum whiskers, fumed silica, nano-calcium carbonate, nano-aluminum nitride, nano-boron nitride and nano-aluminum borate.
  • the defoamers include physical defoamers and/or chemical defoamers. Described physical defoamer is selected from polysiloxane defoamer and/or silicone defoamer, and described chemical defoamer is one selected from calcium oxide, magnesium oxide, calcium hydroxide and latent curing agent. one or more combinations.
  • the defoamer can be the defoamer with the brand name of 066N produced by BYK Chemical, the defoamer 5500 from Deqian Chemical, and the silicone defoamer from Shanghai Tiger.
  • the plasticizers include, but are not limited to, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), chlorinated paraffins, dioctyl adipate Fat, glycol benzoate, trioctyl phosphate, phenyl alkyl sulfonate.
  • DINP Chonese name: diisononyl phthalate
  • DIDP chlorinated paraffin from Danyang Auxiliary Factory
  • vegetable oil from Eaglet dioctyl adipate
  • benzoic acid Optional one or more of glycol ester, trioctyl phosphate and phenyl alkyl sulfonate.
  • the dispersant is a combination of one or more selected from the group consisting of titanate-based dispersants, silane-based dispersants, and carboxylic acid-based dispersants.
  • the dispersing agent may be silane coupling agent WD50 from Hubei Wuda Silicone Company, Hangzhou Lin'an Auxiliary F108 dispersing agent, silane coupling agent KH550, silane coupling agent KH560, Deqian Chemical 9250 dispersing agent, and the like.
  • the reactive diluent is the zoldine RD20 reactive diluent from angus company in the United States.
  • the solvent is No. 230 mineral spirits.
  • the thixotropic agent is fumed silica, Arkema's polyresin wax powder LST.
  • the water scavenger is a molecular sieve and/or an isocyanate water scavenger.
  • it can be p-toluenesulfonyl isocyanate small-molecule water-removing agent from BASF in Germany, Luoyang Jianlong micro-nano molecular sieve.
  • Another technical solution provided by the present invention a use of the above-mentioned polyurethane waterproof coating for spraying construction on a base layer with a temperature of more than 50°C, and the base layer is inclined and/or vertical.
  • the compound represented by the formula (I) in the present invention is prepared by amine methylation of a compound containing an active ⁇ -H phenol, an aldehyde compound and a double-ended primary amine.
  • the compound preferably contains a branched alkylene group; the aldehyde compounds are some common aldehydes, including but not limited to formaldehyde, acetaldehyde, benzaldehyde, and the like.
  • the preparation method of the compound represented by formula (I) of the present invention comprises the following steps:
  • step (b) adding the compound of the double-ended primary amine to be reacted (H 2 NR 1 -NH 2 , R 1 is the same as before) to the reaction solution after the reaction in step (a), mixing, heating up to react, and then vacuum dehydration and/or The temperature is increased for dehydration, and the moisture content is controlled below 500 ppm until a transparent viscous liquid product is obtained, and the compound represented by the formula (I) is prepared.
  • the molar ratio of phenol, aldehyde compound and double-ended primary amine compound is 1:0.5-2:0.5-1.
  • the reaction temperature of the phenol and the aldehyde compound is 50-80°C.
  • step (a) the reaction of the phenol and 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 a molar ratio of 1:0.8-1.2.
  • the reaction temperature after adding the compound of double-ended primary amine is 100-150°C.
  • a preparation method of the above-mentioned polyurethane waterproof coating comprises the following steps:
  • step (2) Mixing the polyurethane prepolymer prepared in step (1) with an auxiliary agent to prepare the polyurethane waterproof coating.
  • adding isocyanate in batches is mainly to ensure that the molecular structure crosslinking density in the early stage is large enough to form polyurea grafting, and provide necessary molecular structure conditions for the thixotropy of the system.
  • step (1) before the first-stage reaction, vacuum dehydration is performed on the polyol and the secondary amine compound, and the moisture content is controlled to be less than 0.05%.
  • step (1) since the first-stage reaction is an exothermic reaction, the first-stage reaction is controlled to stop after the reaction temperature no longer rises and the temperature is stable.
  • the protective gas may be nitrogen gas, argon gas, or the like.
  • step (1) the mass content of NCO in the produced polyurethane prepolymer is controlled to be 2-6%.
  • step (1) in the first-stage reaction, in the first-stage reaction, part of the isocyanates added accounts for 20-50% of the total isocyanates, preferably 20-40%.
  • the auxiliary agent further comprises filler, plasticizer, dispersant, reactive diluent, solvent, thixotropic agent, catalyst, dewatering agent and defoaming agent; wherein The fillers and plasticizers are all dehydrated before being added.
  • step (2) among the auxiliary agents, the plasticizer and the filler are added after the remaining auxiliary agents.
  • step (2) after mixing the polyurethane prepolymer prepared in step (1) with the auxiliary agent, a vacuum defoaming treatment is also performed, and the vacuum defoaming treatment has a vacuum degree of - Carry out under 0.09 ⁇ 0.1MPa.
  • the present invention has the following advantages compared with the prior art:
  • the polyurethane waterproof coating of the present invention innovatively uses a specific secondary amine compound to prepare a polyurethane prepolymer, and the polyurethane prepolymer made from the secondary amine compound has an ideal molecular structure, and itself can have better contact Variable performance (on the one hand, these specific secondary amine-based compounds have a large steric hindrance effect, which can make the reaction mild, and the formed molecular structure is regular and compact; effect, provide more thixotropic contact points, and provide better thixotropy for the system), which can endow waterproof coatings with excellent sag resistance and suitable viscosity, especially for high-temperature base layers, which can still be used with their
  • the special structure achieves both sag resistance and viscosity on the high-temperature base, so that the polyurethane waterproof coating of the present invention can be sprayed by machine, especially sprayed on facades or slopes, which overcomes the problems in summer, etc.
  • This example provides a secondary amine compound of formula (I-1):
  • step (b) adding isopropylene diamine to be reacted (H 2 NC(CH 3 ) 2 -NH 2 , 0.5mol) to the reaction solution after step (a), mixing, heating to 120° C., reacting for 4 hours, and then Vacuum dehydration, control the moisture content below 500ppm, until a transparent viscous liquid product is obtained, and the compound represented by the formula (I-1) is prepared.
  • This example provides a secondary amine compound of formula (I-2):
  • step (b) 3-diaminopentane (H 2 NC(CH 2 CH 3 ) 2 -NH 2 , 0.5 mol) to be reacted was added to the reaction solution after the reaction in step (a), mixed, heated to 120° C., The reaction was carried out for 4 hours, followed by vacuum dehydration, and the moisture content was controlled below 500 ppm until a transparent viscous liquid product was obtained, and the compound represented by the formula (I-2) was prepared.
  • This example provides a secondary amine compound of formula (I-5):
  • step (b) adding isopropylene diamine to be reacted (H 2 NC(CH 3 ) 2 -NH 2 , 0.5mol) to the reaction solution after step (a), mixing, heating to 120° C., reacting for 4 hours, and then Vacuum dehydration is carried out, and the moisture content is controlled below 500 ppm until a transparent viscous liquid product is obtained, and the compound represented by the formula (I-5) is prepared.
  • This example provides a polyurethane waterproof coating, the raw materials of which include: 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 dewatering agent, catalyst 1kg and defoamer 3kg.
  • the raw materials of the polyurethane prepolymer include: 150 kg of Dongda polyether triol 330N, 150 kg of Dongda polyether diol 2000, 20 kg of the secondary amine compound of Example 1, 50 kg of BASF MDI-MI and 50 kg of BASF modified MDI103c.
  • the filler is composed of 150kg Suzhou Rieter ultra-fine LD600 and 100kg Hunan Jinjian B-type nano powder;
  • the plasticizer is 100kg DINP produced by Taiwan Liancheng;
  • the dispersant is 1kg of silane coupling agent WD50 from Hubei Wuhan University Silicone Company;
  • the active diluent is 20kg of zoldine RD20 active diluent from angus company in the United States;
  • the solvent is 100kg No. 230 solvent oil
  • Thixotropic agent is 5kg Deshan PM20L fumed silica
  • the water scavenger is 1kg of p-toluenesulfonyl isocyanate small molecule water scavenger from BASF, Germany;
  • the catalyst is composed of 0.5kg of dibutyltin dilaurate from Beijing Akma, 0.3kg of pentamethyldipropylene triamine from American Air Chemicals, and 0.2kg of zinc isooctanoate from American leading chemicals;
  • the defoamer is composed of 0.5kg of magnesium oxide from Wuxi Zehui Chemical, 0.5kg of calcium oxide from Jiangsu Qunxin, and 2kg of BYK 066N defoamer.
  • the preparation method of polyurethane waterproof coating comprises the following steps:
  • the measured properties are as follows: viscosity 11200mpa.s (25°C), 5800mpa.s (50°C), solid content 88.9%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 4.2MPa, elongation at break 874%, tear strength 23N/mm;
  • Example 4 It is basically the same as Example 4, except that the secondary amine compound is replaced by 22 kg of the compound prepared in Example 2.
  • the measured properties are as follows: viscosity 12100mpa.s (25°C), 6100mpa.s (50°C), solid content 88.8%, surface dry time 2 hours, solid dry time 5 hours, 7 days tensile strength 3.9MPa, elongation at break 976%, tear strength 22N/mm;
  • Example 4 It is basically the same as Example 4, except that the secondary amine compound is replaced by 30.8 kg of the compound prepared in Example 3.
  • the measured properties are as follows: viscosity 13200mpa.s (25°C), 7100mpa.s (50°C), solid content 89%, surface dry time 2 hours, solid dry time 7 hours, 7 days tensile strength 3.8MPa, elongation at break 750%, tear strength 16N/mm;
  • Example 4 Basically the same as Example 4, the difference is only that: in the preparation process of the polyurethane prepolymer, 15kg BASF MDI-MI and 15kg BASF modified MDI103c were added to carry out the first-stage reaction, and then 35kg BASF MDI-MI and 35kg BASF were added. BASF modified MDI103c for the second stage reaction.
  • the measured properties are as follows: viscosity 22000mpa.s (25°C), 12100mpa.s (50°C), solid content 88.9%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 3.1MPa, elongation at break 678%, tear strength 18N/mm;
  • Example 4 Basically the same as Example 4, the difference is only that: the secondary amine compound of Example 1 is replaced by the commercially available chain extender clearlink 1000 4,4'-bis-sec-butylaminodicyclohexylmethane.
  • the measured properties are as follows: viscosity 35000mpa.s (25°C), 21900mpa.s (50°C), solid content 88.8%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 1.1MPa, elongation at break 546%, tear strength 15N/mm; 50°C base surface after mechanical spraying construction is as follows: a thick coating of 1mm flows.
  • Example 4 It is basically the same as Example 4, except that the secondary amine compound in Example 1 is replaced with a commercially available chain extender, methylenebis-o-chloroaniline (moca).
  • a commercially available chain extender methylenebis-o-chloroaniline (moca).
  • the measured properties are as follows: viscosity 45370mpa.s (25°C), 28900mpa.s (50°C), solid content 88.9%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 1.8MPa, elongation at break 457%, tear strength 13N/mm;
  • Example 4 It is basically the same as Example 4, except that the polyurethane prepolymer is prepared by mixing the polyol, the secondary amine compound of Example 1 and all the isocyanates and reacting together at 80 ⁇ 2°C.
  • the measured properties are as follows: viscosity 34600mpa.s (25°C), 17600mpa.s (50°C), solid content 89%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 2.3MPa, elongation at break 478%, tear strength 15N/mm;
  • Example 4 Basically the same as Example 4, the only difference is that the polyurethane prepolymer is prepared by reacting polyol and all isocyanates at 80 ⁇ 2° C. for 2 hours, and then reacting with the secondary amine compound of Example 1 for 1 hour.
  • the measured properties are as follows: viscosity 44900mpa.s (25°C), 22300mpa.s (50°C), solid content 89%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 2.1MPa, elongation at break 786%, tear strength 16N/mm;

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
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Abstract

Disclosed are a polyurethane waterproof coating, a preparation method therefor and the use thereof. The polyurethane waterproof coating comprises a polyurethane prepolymer and an auxiliary agent, wherein the raw material of the polyurethane prepolymer comprises a polyol, an isocyanate and a secondary amine compound, wherein the secondary amine compound is selected from one or a combination of more of the compounds represented by formula (I): wherein R1 is a branched chain alkylene, R2 is H or a C1-10 alkyl, or a C1-10 alkyl substituted by one or more of a C1-6 alkyl and a C1-6 alkoxy, or a phenyl; the polyurethane prepolymer is prepared by mixing the polyol, the secondary amine compound and part of the isocyanate for a reaction, and then adding the rest of the isocyanate for a futher reaction; and the waterproof coating of the present invention is suitable for machine spraying onto a high-temperature base layer, can combine the sagging resistance and viscosity balance, and is especially suitable for spraying construction on a base layer with a temperature of 50ºC or more.

Description

一种聚氨酯防水涂料及其制备方法和应用A kind of polyurethane waterproof coating and its preparation method and application 技术领域technical field
本发明属于建筑防水领域，尤其涉及对于具有较高的温度以及呈立面或斜坡面的建筑基层进行的防水施工，具体涉及一种聚氨酯防水涂料及其应用。The invention belongs to the field of building waterproofing, particularly relates to waterproofing construction for building base layers with high temperature and façades or slopes, in particular to a polyurethane waterproof coating and application thereof.
背景技术Background technique
目前常规的聚氨酯涂料基本为含有溶剂的非环保型涂料，施工时，涂料中的溶剂易挥发，使得环境中味道大，且造成了大气污染。同时，聚氨酯预聚体本身粘度就大，而生产厂家为了降低成本势必要加入填料，造成了涂料的粘度进一步变大，若不加溶剂，则将难以施工应用。目前国内的一些大型工程，如南水北调、大型场馆地下室墙面、高铁、地铁、隧道、人防等，需要在立面或斜坡面进行防水施工，而由于是立面或斜坡面等，使得施工不方便且易出质量问题。用防水涂料可形成无接缝防水层，但是通用型涂料涂刷在立面或斜坡面上时会流淌，造成上部薄、下部厚。上部挂不起厚度，且涂膜表面厚薄不均，若要涂刷1.5mm厚的涂膜，可能需要涂刷四五遍才行。此外，国内夏季大部分区域的气温普遍较高，现场基层太阳暴晒后甚至可达到50℃以上，此时普通型的抗流挂聚氨酯涂料施工立面后容易产生流淌，需要人工多次重复涂刷且每次涂刷后间隔较长时间才可以达到所需厚度，不仅费时费力，而且还极大地浪费了涂料。At present, conventional polyurethane coatings are basically non-environmentally friendly coatings containing solvents. During construction, the solvents in the coatings are volatile, which makes the environment smell bad and causes air pollution. At the same time, the viscosity of the polyurethane prepolymer itself is high, and the manufacturer must add fillers in order to reduce the cost, resulting in a further increase in the viscosity of the coating. If no solvent is added, it will be difficult to apply. At present, some large-scale projects in China, such as the South-to-North Water Transfer Project, basement walls of large venues, high-speed railways, subways, tunnels, civil air defense, etc., need to be waterproofed on the facade or slope, which makes the construction inconvenient. And prone to quality problems. A seamless waterproof layer can be formed with a waterproofing paint, but the general purpose paint will run off when applied to a facade or slope, resulting in a thin upper part and a thick lower part. The thickness of the upper part cannot be hung, and the thickness of the coating film surface is uneven. If you want to apply a 1.5mm thick coating film, you may need to apply it four or five times. In addition, the temperature in most areas of the country in summer is generally high, and the grassroots on site can even reach above 50 °C after exposure to the sun. At this time, ordinary anti-sag polyurethane coatings are prone to flow after the facade is applied, and it needs to be repeatedly painted manually. And it takes a long time to reach the required thickness after each brushing, which is not only time-consuming and labor-intensive, but also a great waste of paint.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明所要解决的技术问题是为了克服现有技术中的不足，提供一种适用于在高温基层上进行喷涂且兼顾抗流挂性和粘度平衡的聚氨酯防水涂料，尤其适用于机器喷涂，基本一次喷涂即可达到要求。In view of this, 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 suitable for spraying on high-temperature base layers and taking into account sag resistance and viscosity balance, especially suitable for machinery. Spraying, basically one spraying can meet the requirements.
本发明同时还提供了一种上述聚氨酯防水涂料的制备方法。The present invention also provides a preparation method of the above-mentioned polyurethane waterproof coating.
本发明同时还提供了一种上述聚氨酯防水涂料在温度达到50℃以上的基层上进行喷涂施工的用途，在该高温基层上进行施工，尤其是在 立面或斜坡面的高温基层上也具有优异的抗流挂性能。At the same time, the present invention also provides the use of the above-mentioned polyurethane waterproof coating for spraying construction on the base layer with a temperature of over 50°C, and the construction on the high-temperature base layer, especially on the high-temperature base layer on the facade or slope surface, also has excellent sag resistance.
为解决以上技术问题，本发明采取的一种技术方案如下：In order to solve the above technical problems, a kind of technical scheme adopted by the present invention is as follows:
一种聚氨酯防水涂料，所述聚氨酯防水涂料包括聚氨酯预聚体和助剂，所述聚氨酯预聚体的原料包括多元醇、异氰酸酯和仲胺化合物，所述仲胺化合物为选自式(Ⅰ)所示化合物中的一种或多种的组合：A polyurethane waterproof coating, the polyurethane waterproof coating comprises a polyurethane prepolymer and an auxiliary, the raw materials of the polyurethane prepolymer include polyol, isocyanate and secondary amine compound, and the secondary amine compound is selected from formula (I) Combinations of one or more of the compounds shown:
Figure PCTCN2021102729-appb-000001
Figure PCTCN2021102729-appb-000001
其中，R 1为支链亚烷基； Wherein, R 1 is branched alkylene;
R 2为H或C 1-10烷基，或为被选自C 1-6烷基、C 1-6烷氧基中的一个或多个所取代的C 1-10烷基或苯基； R 2 is H or C 1-10 alkyl, or C 1-10 alkyl or phenyl substituted by one or more selected from C 1-6 alkyl, C 1-6 alkoxy;
所述聚氨酯预聚体通过使多元醇、仲胺化合物和部分异氰酸酯混合反应后再加入剩余异氰酸酯再次反应而制成。The polyurethane prepolymer is prepared by mixing and reacting polyol, secondary amine compound and part of isocyanate, and then adding the remaining isocyanate to react again.
根据本发明的一些优选方面，R 1为C 3-10支链亚烷基，R 1可以为-C(CH 3) 2-、-C(CH 2CH 3) 2-、-C(CH 2CH 2CH 3) 2-、-CH(CH 3)-、-CH(CH 2CH 3)-、-C{CH(CH 3) 2} 2-、-C{CH(CH 2CH 3) 2} 2-、-C{CH 2CH(CH 3) 2} 2-、-C{CH 2CH 2CH(CH 3) 2} 2-等等。 According to some preferred aspects of the present invention, R 1 is C 3-10 branched chain alkylene, and R 1 can be -C(CH 3 ) 2 -, -C(CH 2 CH 3 ) 2 -, -C(CH 2 CH 2 CH 3 ) 2 -, -CH(CH 3 )-, -CH(CH 2 CH 3 )-, -C{CH(CH 3 ) 2 } 2 -, -C{CH(CH 2 CH 3 ) 2 } 2 -, -C{CH 2 CH(CH 3 ) 2 } 2 -, -C{CH 2 CH 2 CH(CH 3 ) 2 } 2 - and so on.
根据本发明的一些优选方面，R 2为H、甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、甲氧基甲基、甲氧基乙基、甲氧基丙基、甲氧基异丙基、甲氧基丁基、甲氧基异丁基、甲氧基戊基、乙氧基甲基、乙氧基乙基、乙氧基丙基、乙氧基异丙基、乙氧基丁基、乙氧基异丁基、乙氧基戊基、甲基苯基、乙基苯基、甲氧基苯基、乙氧基苯基或苯基。 According to some preferred aspects of the invention, R 2 is H, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, methoxymethyl, methoxyethyl, methoxy methoxypropyl, methoxyisopropyl, methoxybutyl, methoxyisobutyl, methoxypentyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxy isopropyl, ethoxybutyl, ethoxyisobutyl, ethoxypentyl, methylphenyl, ethylphenyl, methoxyphenyl, ethoxyphenyl or phenyl.
根据本发明的一些优选且具体的方面，所述仲胺化合物为选自下式结构所示化合物中的一种或多种的组合：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 compounds represented by the following formula:
Figure PCTCN2021102729-appb-000002
Figure PCTCN2021102729-appb-000002
Figure PCTCN2021102729-appb-000003
Figure PCTCN2021102729-appb-000003
根据本发明的一些优选方面，所述多元醇、所述异氰酸酯和所述式(Ⅰ)所示化合物的投料质量比为1∶0.2-0.5∶0.05-0.15。According to some preferred aspects of the present invention, the mass ratio of the polyol, the isocyanate and the compound represented by the formula (I) is 1:0.2-0.5:0.05-0.15.
根据本发明的一些优选方面，所述多元醇由二元醇和三元醇构成， 所述二元醇与所述三元醇的投料质量比为1∶0.1-1。例如可以为山东东大化学工业有限公司生产的聚醚330N、聚醚4000，聚醚2000、聚醚3050，聚醚1000，聚醚400。According to some preferred aspects of the present invention, 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. For example, it can be polyether 330N, polyether 4000, polyether 2000, polyether 3050, polyether 1000, and polyether 400 produced by Shandong Dongda Chemical Industry Co., Ltd.
根据本发明的一些优选方面，所述异氰酸酯为多异氰酸酯。According to some preferred aspects of the present invention, the isocyanate is a polyisocyanate.
根据本发明的一些优选且具体的方面，所述多异氰酸酯为选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、改性二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯和六亚甲基二异氰酸酯中至少两种的组合。例如可以为选自为德国巴斯夫公司生产的牌号为MDI-MI的二苯基甲烷二异氰酸酯、万华化学的MDI50，万华化学的MDI100，万华化学的IPDI、万华化学的HDI，巴斯夫的改性MDI 103C，德国拜耳公司牌号为TDI-80的甲苯二异氰酸酯中的至少两种。According to some preferred and specific aspects of the present invention, the polyisocyanate is selected from toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, modified diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate A combination of at least two of isocyanate and hexamethylene diisocyanate. For example, it can be selected from the MDI-MI diphenylmethane diisocyanate produced by BASF in Germany, MDI50 of Wanhua Chemical, MDI100 of Wanhua Chemical, IPDI of Wanhua Chemical, HDI of Wanhua Chemical, BASF's Modified MDI 103C, at least two of the toluene diisocyanates with the brand name of TDI-80 from Bayer, Germany.
根据本发明的一些优选方面，制备所述聚氨酯预聚体的过程中，所述多元醇、所述仲胺化合物和所述部分异氰酸酯的混合反应的温度小于等于60℃。According to some preferred aspects of the present invention, in the process of preparing the polyurethane prepolymer, the temperature of the mixing reaction of the polyol, the secondary amine compound and the partial isocyanate is less than or equal to 60°C.
根据本发明的一些优选方面，制备所述聚氨酯预聚体的过程中，加入剩余异氰酸酯后的反应温度为75-85℃。According to some preferred aspects of the present invention, in the process of preparing the polyurethane prepolymer, the reaction temperature after adding the remaining isocyanate is 75-85°C.
本发明中，对于聚氨酯预聚体合成过程中温度的控制，有利于控制反应进行的程度以形成预期的分子结构，确保高温下的抗流挂与粘性平衡，同时有利于喷涂施工。In the present invention, the temperature control during the synthesis of the polyurethane prepolymer is beneficial to control the degree of reaction to form the expected molecular structure, to ensure the balance between sag resistance and viscosity at high temperature, and at the same time, it is beneficial to spray construction.
根据本发明的一些优选方面，所述助剂包括催化剂，所述催化剂由投料质量比为1∶0.4-0.8∶0.2-0.6的二月桂酸二丁基锡、五甲基二亚丙基三胺和异辛酸锌构成。According to some preferred aspects of the present invention, the auxiliary agent comprises a catalyst, and the catalyst is composed of dibutyltin dilaurate, pentamethyldipropylenetriamine and isopropylamine with a mass ratio of 1:0.4-0.8:0.2-0.6. Zinc octoate composition.
根据本发明的一些具体且优选的方面，所述助剂还包括填料、增塑剂、分散剂、活性稀释剂、溶剂、触变剂、除水剂和消泡剂；以质量份数计，所述聚氨酯防水涂料中，聚氨酯预聚体20-50份、填料20-50份、增塑剂5-30份、分散剂0.1-1份、活性稀释剂0.3-2份、溶剂0.5-15份、触变剂0.1-2份、除水剂0.1-1份、催化剂0.05-1份和消泡剂0.1-1份。According to some specific and preferred aspects of the present invention, the adjuvant further includes filler, plasticizer, dispersant, reactive diluent, solvent, thixotropic agent, dewatering agent and defoaming agent; in parts by mass, In the polyurethane waterproof coating, 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 reactive diluent, and 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 defoamer.
根据本发明的一些具体方面，所述填料包括重质填料和/或纳米级填料。所述重质填料为选自钛白粉、重质碳酸钙、高岭土、滑石粉中的 一种或多种的组合。所述纳米级填料为选自石膏晶须、气相二氧化硅、纳米碳酸钙、纳米氮化铝、纳米氮化硼和纳米硼酸铝中的一种或多种的组合。According to some specific aspects of the present invention, the fillers include heavy fillers and/or nanoscale fillers. The heavy filler is one or more combinations selected from titanium dioxide, heavy calcium carbonate, kaolin, and talc. The nano-scale filler is a combination of one or more selected from gypsum whiskers, fumed silica, nano-calcium carbonate, nano-aluminum nitride, nano-boron nitride and nano-aluminum borate.
根据本发明的一些具体方面，所述消泡剂包括物理消泡剂和/或化学消泡剂。所述物理消泡剂为选自聚硅氧烷消泡剂和/或硅酮消泡剂，所述化学消泡剂为选自氧化钙、氧化镁、氢氧化钙和潜固化剂中的一种或多种的组合。所述消泡剂可以为毕克化学公司生产的牌号为066N的消泡剂，德谦化学的消泡剂5500，上海泰格公司的有机硅消泡剂。According to some specific aspects of the present invention, the defoamers include physical defoamers and/or chemical defoamers. Described physical defoamer is selected from polysiloxane defoamer and/or silicone defoamer, and described chemical defoamer is one selected from calcium oxide, magnesium oxide, calcium hydroxide and latent curing agent. one or more combinations. The defoamer can be the defoamer with the brand name of 066N produced by BYK Chemical, the defoamer 5500 from Deqian Chemical, and the silicone defoamer from Shanghai Tiger.
根据本发明的一些具体方面，所述增塑剂包括但不限于邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二异癸酯(DIDP)、氯化石蜡、己二酸二辛脂、苯甲酸二醇酯、磷酸三辛酯、烷基磺酸苯酯。例如可以是中国台湾联成的DINP(中文名称：邻苯二甲酸二异壬酯)、DIDP、丹阳助剂厂的氯化石蜡、伊格特的植物油脂，己二酸二辛脂，苯甲酸二醇酯，磷酸三辛酯，烷基磺酸苯酯中任选一种或几种。According to some specific aspects of the present invention, the plasticizers include, but are not limited to, diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), chlorinated paraffins, dioctyl adipate Fat, glycol benzoate, trioctyl phosphate, phenyl alkyl sulfonate. For example, it can be DINP (Chinese name: diisononyl phthalate) from Taiwan, China, DIDP, chlorinated paraffin from Danyang Auxiliary Factory, vegetable oil from Eaglet, dioctyl adipate, benzoic acid Optional one or more of glycol ester, trioctyl phosphate and phenyl alkyl sulfonate.
根据本发明的一些具体方面，所述分散剂为选自钛酸酯类分散剂、硅烷类分散剂和羧酸类分散剂中的一种或多种的组合。例如所述分散剂可以为湖北武大有机硅公司的硅烷偶联剂WD50，杭州临安助剂f108分散剂，硅烷偶联剂KH550，硅烷偶联剂KH560，德谦化学9250分散剂等。According to some specific aspects of the present invention, the dispersant is a combination of one or more selected from the group consisting of titanate-based dispersants, silane-based dispersants, and carboxylic acid-based dispersants. For example, the dispersing agent may be silane coupling agent WD50 from Hubei Wuda Silicone Company, Hangzhou Lin'an Auxiliary F108 dispersing agent, silane coupling agent KH550, silane coupling agent KH560, Deqian Chemical 9250 dispersing agent, and the like.
根据本发明的一些具体方面，所述活性稀释剂为美国angus公司的zoldine RD20活性稀释剂。According to some specific aspects of the present invention, the reactive diluent is the zoldine RD20 reactive diluent from angus company in the United States.
根据本发明的一些具体方面，所述溶剂为230号溶剂油。According to some specific aspects of the invention, the solvent is No. 230 mineral spirits.
根据本发明的一些具体方面，所述触变剂为气相二氧化硅，阿科玛的聚树脂蜡粉LST。According to some specific aspects of the present invention, the thixotropic agent is fumed silica, Arkema's polyresin wax powder LST.
根据本发明的一些具体方面，所述除水剂为分子筛和/或异氰酸酯除水剂。例如可以是德国巴斯夫的对甲苯磺酰异氰酸酯小分子除水剂、洛阳建龙微纳分子筛。According to some specific aspects of the present invention, the water scavenger is a molecular sieve and/or an isocyanate water scavenger. For example, it can be p-toluenesulfonyl isocyanate small-molecule water-removing agent from BASF in Germany, Luoyang Jianlong micro-nano molecular sieve.
本发明提供的又一技术方案：一种上述所述的聚氨酯防水涂料在温度达到50℃以上的基层上进行喷涂施工的用途，所述基层为倾斜设置 和/或竖直设置。Another technical solution provided by the present invention: a use of the above-mentioned polyurethane waterproof coating for spraying construction on a base layer with a temperature of more than 50°C, and the base layer is inclined and/or vertical.
根据本发明，本发明中的式(Ⅰ)所示化合物通过利用含有活泼的α-H的苯酚与醛类化合物及双端伯胺的化合物经过胺甲基化反应制成，双端伯胺的化合物优选含有支链亚烷基；醛类化合物为常见的一些醛，包括但不限于甲醛、乙醛、苯甲醛等等。优选地，本发明的式(Ⅰ)所示化合物的制备方法包括如下步骤：According to the present invention, the compound represented by the formula (I) in the present invention is prepared by amine methylation of a compound containing an active α-H phenol, an aldehyde compound and a double-ended primary amine. The compound preferably contains a branched alkylene group; the aldehyde compounds are some common aldehydes, including but not limited to formaldehyde, acetaldehyde, benzaldehyde, and the like. Preferably, the preparation method of the compound represented by formula (I) of the present invention comprises the following steps:
(a)使苯酚与醛类化合物，升温反应；(a) make phenol and aldehyde compound, temperature rise reaction;
(b)向步骤(a)反应后的反应液中加入要反应的双端伯胺的化合物(H 2N-R 1-NH 2，R 1同前)，混合，升温反应，然后真空脱水和/或升温脱水，控制水分含量500ppm以下，直到得到透明粘稠状液体产品，制成所述式(Ⅰ)所示化合物。 (b) adding the compound of the double-ended primary amine to be reacted (H 2 NR 1 -NH 2 , R 1 is the same as before) to the reaction solution after the reaction in step (a), mixing, heating up to react, and then vacuum dehydration and/or The temperature is increased for dehydration, and the moisture content is controlled below 500 ppm until a transparent viscous liquid product is obtained, and the compound represented by the formula (I) is prepared.
优选地，苯酚、醛类化合物和双端伯胺的化合物(H 2N-R 1-NH 2)的投料摩尔比为1∶0.5-2∶0.5-1。 Preferably, the molar ratio of phenol, aldehyde compound and double-ended primary amine compound (H 2 NR 1 -NH 2 ) is 1:0.5-2:0.5-1.
优选地，步骤(a)中，苯酚与醛类化合物的反应温度为50-80℃。Preferably, in step (a), the reaction temperature of the phenol and the aldehyde compound is 50-80°C.
优选地，步骤(a)中，使苯酚与醛类化合物的反应在碱土金属镁型催化剂存在下进行。所述碱土金属镁型催化剂由投料摩尔比为1∶0.8-1.2的氢氧化镁和氧化镁构成。Preferably, in step (a), the reaction of the phenol and 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 a molar ratio of 1:0.8-1.2.
优选地，步骤(b)中，加入双端伯胺的化合物(H 2N-R 1-NH 2)之后的反应温度为100-150℃。 Preferably, in step (b), the reaction temperature after adding the compound of double-ended primary amine (H 2 NR 1 -NH 2 ) is 100-150°C.
本发明提供的又一技术方案：一种上述所述的聚氨酯防水涂料的制备方法，所述制备方法包括如下步骤：Another technical solution provided by the present invention: a preparation method of the above-mentioned polyurethane waterproof coating, the preparation method comprises the following steps:
(1)制备聚氨酯预聚体(1) Preparation of polyurethane prepolymer
将多元醇与上述特定的仲胺化合物混合，加入部分异氰酸酯，在温度为60℃以下的条件下进行第一阶段反应；然后加入剩余异氰酸酯，升温至75-85℃，进行第二阶段反应，制成聚氨酯预聚体；其中，所述第一阶段反应、所述第二阶段反应分别在保护气体保护下进行；Mix the polyol with the above-mentioned specific secondary amine compound, add part of the isocyanate, and carry out the first-stage reaction under the condition that the temperature is below 60 ° C; then add the remaining isocyanate, heat up to 75-85 ° C, and carry out the second-stage reaction. into a polyurethane prepolymer; wherein, the first-stage reaction and the second-stage reaction are carried out under the protection of protective gas;
(2)将步骤(1)制成的聚氨酯预聚体与助剂混合，制成所述聚氨酯防水涂料。(2) Mixing the polyurethane prepolymer prepared in step (1) with an auxiliary agent to prepare the polyurethane waterproof coating.
本发明中，分批加入异氰酸酯主要是为了确保前期分子结构交联密 度足够大，形成聚脲接枝，为体系触变性提供必要的分子结构条件。In the present invention, adding isocyanate in batches is mainly to ensure that the molecular structure crosslinking density in the early stage is large enough to form polyurea grafting, and provide necessary molecular structure conditions for the thixotropy of the system.
根据本发明的一些优选方面，步骤(1)中，在进行所述第一阶段反应之前，先对所述多元醇和所述仲胺化合物进行真空脱水操作，并控制水分含量低于0.05％。According to some preferred aspects of the present invention, in step (1), before the first-stage reaction, vacuum dehydration is performed on the polyol and the secondary amine compound, and the moisture content is controlled to be less than 0.05%.
根据本发明的一些优选方面，步骤(1)中，由于所述第一阶段反应为放热反应，因此控制所述第一阶段反应在反应温度不再上升且温度稳定后停止。According to some preferred aspects of the present invention, in step (1), since the first-stage reaction is an exothermic reaction, the first-stage reaction is controlled to stop after the reaction temperature no longer rises and the temperature is stable.
根据本发明的一些优选方面，步骤(1)中，所述保护气体可以为氮气、氩气等等。According to some preferred aspects of the present invention, in step (1), the protective gas may be nitrogen gas, argon gas, or the like.
根据本发明的一些优选方面，步骤(1)中，控制制成的所述聚氨酯预聚体的NCO的质量含量为2-6％。According to some preferred aspects of the present invention, in step (1), the mass content of NCO in the produced polyurethane prepolymer is controlled to be 2-6%.
根据本发明的一些优选方面，步骤(1)中，以质量百分含量计，所述第一阶段反应中，加入的部分异氰酸酯占总的异氰酸酯的20-50％，优选为20-40％。According to some preferred aspects of the present invention, in step (1), in the first-stage reaction, in the first-stage reaction, part of the isocyanates added accounts for 20-50% of the total isocyanates, preferably 20-40%.
根据本发明的一些优选方面，步骤(2)中，所述助剂还包括填料、增塑剂、分散剂、活性稀释剂、溶剂、触变剂、催化剂、除水剂和消泡剂；其中所述填料、增塑剂在添加前均进行脱水处理。According to some preferred aspects of the present invention, in step (2), the auxiliary agent further comprises filler, plasticizer, dispersant, reactive diluent, solvent, thixotropic agent, catalyst, dewatering agent and defoaming agent; wherein The fillers and plasticizers are all dehydrated before being added.
根据本发明的一些优选方面，步骤(2)中，所述助剂中，所述增塑剂与所述填料在其余助剂之后添加。According to some preferred aspects of the present invention, in step (2), among the auxiliary agents, the plasticizer and the filler are added after the remaining auxiliary agents.
根据本发明的一些优选方面，步骤(2)中，将步骤(1)制成的聚氨酯预聚体与助剂混合之后，还进行真空脱泡处理，所述真空脱泡处理在真空度为-0.09～0.1MPa下进行。According to some preferred aspects of the present invention, in step (2), after mixing the polyurethane prepolymer prepared in step (1) with the auxiliary agent, a vacuum defoaming treatment is also performed, and the vacuum defoaming treatment has a vacuum degree of - Carry out under 0.09～0.1MPa.
由于以上技术方案的采用，本发明与现有技术相比具有如下优点：Due to the adoption of the above technical solutions, the present invention has the following advantages compared with the prior art:
本发明的聚氨酯防水涂料，创新地采用特定的仲胺化合物进行制备聚氨酯预聚体，由此仲胺化合物制成的聚氨酯预聚体具有理想的分子结构，且其本身就能够具有较好的触变性能(这些特定的仲胺基化合物一方面有较大的位阻效应，可以使得反应温和，形成的分子结构规整致密，另一方面结构对称且分子结构较为舒展，可充分地利用氢键的作用，提供较多触变性的接触点，为体系提供较好的触变性)，其能够赋予防水 涂料极佳的抗流挂性能和适宜的粘度，尤其是对于高温的基层，其仍然能够以其特殊的结构在高温基层上实现兼顾抗流挂性能和粘度，从而使得本发明的聚氨酯防水涂料能够采用机器进行喷涂施工，尤其是在立面或斜坡面上进行喷涂施工，克服了在诸如夏季等等外界因素造成的基层温度太高而难以进行喷涂防水涂料的缺陷。The polyurethane waterproof coating of the present invention innovatively uses a specific secondary amine compound to prepare a polyurethane prepolymer, and the polyurethane prepolymer made from the secondary amine compound has an ideal molecular structure, and itself can have better contact Variable performance (on the one hand, these specific secondary amine-based compounds have a large steric hindrance effect, which can make the reaction mild, and the formed molecular structure is regular and compact; effect, provide more thixotropic contact points, and provide better thixotropy for the system), which can endow waterproof coatings with excellent sag resistance and suitable viscosity, especially for high-temperature base layers, which can still be used with their The special structure achieves both sag resistance and viscosity on the high-temperature base, so that the polyurethane waterproof coating of the present invention can be sprayed by machine, especially sprayed on facades or slopes, which overcomes the problems in summer, etc. The temperature of the base layer caused by external factors is too high and it is difficult to spray the waterproof coating.
具体实施方式Detailed ways
以下结合具体实施例对上述方案做进一步说明；应理解，这些实施例是用于说明本发明的基本原理、主要特征和优点，而本发明不受以下实施例的范围限制；实施例中采用的实施条件可以根据具体要求做进一步调整，未注明的实施条件通常为常规实验中的条件。The above scheme will be further described below in conjunction with specific examples; it should be understood that these examples are used to illustrate the basic principles, main features and advantages of the present invention, and the present invention is not limited by the scope of the following examples; The implementation conditions can be further adjusted according to specific requirements, and the unspecified implementation conditions are usually those in routine experiments.
下述实施例中，如无特别说明，所有原料均来自于商购或者通过本领域的常规方法制备而得。In the following examples, unless otherwise specified, all raw materials were obtained from commercial sources or prepared by conventional methods in the art.
实施例1Example 1
本例提供一种式(Ⅰ-1)所示结构的仲胺化合物：This example provides a secondary amine compound of formula (I-1):
Figure PCTCN2021102729-appb-000004
Figure PCTCN2021102729-appb-000004
其制备方法包括如下步骤：Its preparation method comprises the following steps:
(a)使苯酚(1mol)、质量分数为37％的甲醛水溶液(含有甲醛2mol)、碱土金属镁型催化剂0.05mol(由投料摩尔比为1∶1的氢氧化镁和氧化镁构成)混合，升温至60℃，反应1h；(a) mixing phenol (1 mol), a 37% aqueous formaldehyde solution (containing 2 mol of formaldehyde), and 0.05 mol of an alkaline earth metal magnesium type catalyst (consisting of magnesium hydroxide and magnesium oxide whose molar ratio is 1:1), The temperature was raised to 60°C and the reaction was carried out for 1h;
(b)向步骤(a)反应后的反应液中加入要反应的异丙二胺(H 2N-C(CH 3) 2-NH 2，0.5mol)，混合，升温至120℃，反应4h，然后真空脱水，控制水分含量500ppm以下，直到得到透明粘稠状液体产品，制成所述式(Ⅰ-1)所示化合物。 (b) adding isopropylene diamine to be reacted (H 2 NC(CH 3 ) 2 -NH 2 , 0.5mol) to the reaction solution after step (a), mixing, heating to 120° C., reacting for 4 hours, and then Vacuum dehydration, control the moisture content below 500ppm, until a transparent viscous liquid product is obtained, and the compound represented by the formula (I-1) is prepared.
实施例2Example 2
本例提供一种式(Ⅰ-2)所示结构的仲胺化合物：This example provides a secondary amine compound of formula (I-2):
Figure PCTCN2021102729-appb-000005
Figure PCTCN2021102729-appb-000005
其制备方法包括如下步骤：Its preparation method comprises the following steps:
(a)使苯酚(1mol)、质量分数为37％的甲醛水溶液(含有甲醛2mol)、碱土金属镁型催化剂0.05mol(由投料摩尔比为1∶1的氢氧化镁和氧化镁构成)混合，升温至60℃，反应1h；(a) mixing phenol (1 mol), a 37% aqueous formaldehyde solution (containing 2 mol of formaldehyde), and 0.05 mol of an alkaline earth metal magnesium type catalyst (consisting of magnesium hydroxide and magnesium oxide whose molar ratio is 1:1), The temperature was raised to 60°C and the reaction was carried out for 1h;
(b)向步骤(a)反应后的反应液中加入要反应的3-二氨基戊烷(H 2N-C(CH 2CH 3) 2-NH 2，0.5mol)，混合，升温至120℃，反应4h，然后真空脱水，控制水分含量500ppm以下，直到得到透明粘稠状液体产品，制成所述式(Ⅰ-2)所示化合物。 (b) 3-diaminopentane (H 2 NC(CH 2 CH 3 ) 2 -NH 2 , 0.5 mol) to be reacted was added to the reaction solution after the reaction in step (a), mixed, heated to 120° C., The reaction was carried out for 4 hours, followed by vacuum dehydration, and the moisture content was controlled below 500 ppm until a transparent viscous liquid product was obtained, and the compound represented by the formula (I-2) was prepared.
实施例3Example 3
本例提供一种式(Ⅰ-5)所示结构的仲胺化合物：This example provides a secondary amine compound of formula (I-5):
Figure PCTCN2021102729-appb-000006
Figure PCTCN2021102729-appb-000006
其制备方法包括如下步骤：Its preparation method comprises the following steps:
(a)使苯酚(1mol)、苯甲醛(2mol)、碱土金属镁型催化剂0.05mol(由投料摩尔比为1∶1的氢氧化镁和氧化镁构成)混合，升温至80℃，反应1h；(a) mix phenol (1mol), benzaldehyde (2mol), alkaline earth metal magnesium type catalyst 0.05mol (consisting of magnesium hydroxide and magnesium oxide with a molar ratio of 1:1), be warming up to 80°C, and react for 1h;
(b)向步骤(a)反应后的反应液中加入要反应的异丙二胺(H 2N-C(CH 3) 2-NH 2，0.5mol)，混合，升温至120℃，反应4h，然后真空脱水，控制水分含量500ppm以下，直到得到透明粘稠状液体产品，制成所述式(Ⅰ-5)所示化合物。 (b) adding isopropylene diamine to be reacted (H 2 NC(CH 3 ) 2 -NH 2 , 0.5mol) to the reaction solution after step (a), mixing, heating to 120° C., reacting for 4 hours, and then Vacuum dehydration is carried out, and the moisture content is controlled below 500 ppm until a transparent viscous liquid product is obtained, and the compound represented by the formula (I-5) is prepared.
实施例4Example 4
本例提供一种聚氨酯防水涂料，其原料包括：聚氨酯预聚体420kg、 填料250kg、增塑剂100kg、分散剂1kg、活性稀释剂20kg、溶剂100kg、触变剂5kg、除水剂1kg、催化剂1kg和消泡剂3kg。This example provides a polyurethane waterproof coating, the raw materials of which include: 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 dewatering agent, catalyst 1kg and defoamer 3kg.
聚氨酯预聚体的原料包括：150kg东大聚醚三元醇330N、150kg东大聚醚二元醇2000、20kg实施例1的仲胺化合物、50kg巴斯夫MDI-MI和50kg巴斯夫改性MDI103c。The raw materials of the polyurethane prepolymer include: 150 kg of Dongda polyether triol 330N, 150 kg of Dongda polyether diol 2000, 20 kg of the secondary amine compound of Example 1, 50 kg of BASF MDI-MI and 50 kg of BASF modified MDI103c.
填料由150kg苏州立达超微LD600和100kg湖南金箭B型纳米粉构成；The filler is composed of 150kg Suzhou Rieter ultra-fine LD600 and 100kg Hunan Jinjian B-type nano powder;
增塑剂为100kg台湾联成产的DINP；The plasticizer is 100kg DINP produced by Taiwan Liancheng;
分散剂为1kg湖北武大有机硅公司的硅烷偶联剂WD50；The dispersant is 1kg of silane coupling agent WD50 from Hubei Wuhan University Silicone Company;
活性稀释剂为20kg美国angus公司的zoldine RD20活性稀释剂；The active diluent is 20kg of zoldine RD20 active diluent from angus company in the United States;
溶剂为100kg230号溶剂油；The solvent is 100kg No. 230 solvent oil;
触变剂为5kg德山PM20L气硅；Thixotropic agent is 5kg Deshan PM20L fumed silica;
除水剂为1kg德国巴斯夫的对甲苯磺酰异氰酸酯小分子除水剂；The water scavenger is 1kg of p-toluenesulfonyl isocyanate small molecule water scavenger from BASF, Germany;
催化剂由0.5kg北京阿克玛的二月桂酸二丁基锡、0.3kg美国空气化工的五甲基二亚丙基三胺、0.2kg美国领先化学的异辛酸锌构成；The catalyst is composed of 0.5kg of dibutyltin dilaurate from Beijing Akma, 0.3kg of pentamethyldipropylene triamine from American Air Chemicals, and 0.2kg of zinc isooctanoate from American leading chemicals;
消泡剂由0.5kg无锡泽辉化工的氧化镁、0.5kg江苏群鑫的氧化钙、2kg毕克化学066N的消泡剂构成。The defoamer is composed of 0.5kg of magnesium oxide from Wuxi Zehui Chemical, 0.5kg of calcium oxide from Jiangsu Qunxin, and 2kg of BYK 066N defoamer.
聚氨酯防水涂料的制备方法包括如下步骤：The preparation method of polyurethane waterproof coating comprises the following steps:
(1)聚氨酯预聚体的制备：(1) Preparation of polyurethane prepolymer:
将150kg东大聚醚三元醇330N、150kg东大聚醚二元醇2000、与20kg实施例1的仲胺化合物混合，在搅拌状态下慢慢升温到120℃，真空脱水2h，直至水分含量小于0.05％；Mix 150kg of Dongda polyether triol 330N, 150kg of Dongda polyether diol 2000, and 20kg of the secondary amine compound of Example 1, slowly raise the temperature to 120°C under stirring, and dehydrate under vacuum for 2 hours until the moisture content less than 0.05%;
将温度降低到60℃以下，加入10kg巴斯夫MDI-MI和10kg巴斯夫改性MDI103c，在温度为60℃以下的条件下进行第一阶段反应，待反应温度不再上升且稳定后，加入40kg巴斯夫MDI-MI和40kg巴斯夫改性MDI103c，升温至80±2℃，保温进行第二阶段反应，直至NCO的质量含量为3.8％，中止反应，制成聚氨酯预聚体；其中，所述第一阶段反应、所述第二阶段反应分别在氮气保护下进行；Lower the temperature to below 60°C, add 10kg of BASF MDI-MI and 10kg of BASF modified MDI103c, and carry out the first-stage reaction at a temperature below 60°C. After the reaction temperature no longer rises and stabilizes, add 40kg of BASF MDI -MI and 40kg of BASF-modified MDI103c, heat up to 80±2°C, keep warm to carry out the second-stage reaction, until the mass content of NCO is 3.8%, stop the reaction, and make a polyurethane prepolymer; wherein, the first-stage reaction , the second stage reaction is carried out under nitrogen protection respectively;
(2)按配方量将按照步骤(1)制成的聚氨酯预聚体与5kg德山 PM20L气硅，0.5kg无锡泽辉化工的氧化镁和0.5kg江苏群鑫的氧化钙，100kg230号溶剂油，20kg美国angus公司的zoldine RD20活性稀释剂，2kg毕克化学066N的消泡剂，1kg湖北武大有机硅公司的硅烷偶联剂WD50，0.5kg北京阿克玛的二月桂酸二丁基锡，0.3kg美国空气化工的五甲基二亚丙基三胺，0.2kg美国领先化学的异辛酸锌，0.5kg德国巴斯夫的对甲苯磺酰异氰酸酯小分子除水剂充分混合，然后再加入脱水后的100kg台湾联成产的DINP增塑剂、150kg苏州立达超微LD600、100kg湖南金箭B型纳米碳酸钙，混合，并于0.04±0.02MPa的真空度下脱泡1h后，通过刮板细度仪测试细度达到50μm，制成所述聚氨酯防水涂料。(2) the polyurethane prepolymer made according to step (1) and 5kg of Deshan PM20L fumed silica, 0.5kg of magnesium oxide of Wuxi Zehui Chemical Industry and 0.5kg of calcium oxide of Jiangsu Qunxin, 100kg of No. 230 solvent oil by formula amount , 20kg of zoldine RD20 reactive diluent from American Angus Company, 2kg of BYK 066N defoamer, 1kg of silane coupling agent WD50 from Hubei Wuda Silicone Company, 0.5kg of Beijing Akma's dibutyltin dilaurate, 0.3kg Pentamethyldipropylene triamine from American Air Chemicals, 0.2kg of Zinc Iso-Octanoate from America's leading chemical industry, and 0.5kg of p-toluenesulfonyl isocyanate small-molecule water scavenger from BASF in Germany were mixed thoroughly, and then 100kg of dehydrated Taiwan DINP plasticizer produced by Liancheng, 150kg Suzhou Rieter ultra-fine LD600, and 100kg Hunan Jinjian B-type nano-calcium carbonate were mixed and degassed under a vacuum of 0.04±0.02MPa for 1 hour, and then passed through a scraper fineness meter. The test fineness reaches 50 μm, and the polyurethane waterproof coating is prepared.
测得性能如下：粘度11200mpa.s(25℃)，5800mpa.s(50℃)，固含量88.9％，表干时间2小时，实干时间6小时，7天拉伸强度4.2MPa，断裂伸长率874％，撕裂强度23N/mm；The measured properties are as follows: viscosity 11200mpa.s (25℃), 5800mpa.s (50℃), solid content 88.9%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 4.2MPa, elongation at break 874%, tear strength 23N/mm;
50℃基面机械喷涂施工后情况如下：一次厚涂1.5mm不流淌。The situation after mechanical spraying on the base surface at 50°C is as follows: a thick coating of 1.5mm does not flow.
实施例5Example 5
基本同实施例4，其区别仅在于：将仲胺化合物替换为22kg实施例2制成的化合物。测得性能如下：粘度12100mpa.s(25℃)，6100mpa.s(50℃)，固含量88.8％，表干时间2小时，实干时间5小时，7天拉伸强度3.9MPa，断裂伸长率976％，撕裂强度22N/mm；It is basically the same as Example 4, except that the secondary amine compound is replaced by 22 kg of the compound prepared in Example 2. The measured properties are as follows: viscosity 12100mpa.s (25℃), 6100mpa.s (50℃), solid content 88.8%, surface dry time 2 hours, solid dry time 5 hours, 7 days tensile strength 3.9MPa, elongation at break 976%, tear strength 22N/mm;
50℃基面机械喷涂施工后情况如下：一次厚涂1.5mm不流淌。The situation after mechanical spraying on the base surface at 50°C is as follows: a thick coating of 1.5mm does not flow.
实施例6Example 6
基本同实施例4，其区别仅在于：将仲胺化合物替换为30.8kg实施例3制成的化合物。It is basically the same as Example 4, except that the secondary amine compound is replaced by 30.8 kg of the compound prepared in Example 3.
测得性能如下：粘度13200mpa.s(25℃)，7100mpa.s(50℃)，固含量89％，表干时间2小时，实干时间7小时，7天拉伸强度3.8MPa，断裂伸长率750％，撕裂强度16N/mm；The measured properties are as follows: viscosity 13200mpa.s (25℃), 7100mpa.s (50℃), solid content 89%, surface dry time 2 hours, solid dry time 7 hours, 7 days tensile strength 3.8MPa, elongation at break 750%, tear strength 16N/mm;
50℃基面机械喷涂施工后情况如下：一次厚涂1.5mm不流淌。The situation after mechanical spraying on the base surface at 50°C is as follows: a thick coating of 1.5mm does not flow.
实施例7Example 7
基本同实施例4，其区别仅在于：在聚氨酯预聚体的制备过程中，先加入15kg巴斯夫MDI-MI和15kg巴斯夫改性MDI103c进行第一阶 段反应，然后再加入35kg巴斯夫MDI-MI和35kg巴斯夫改性MDI103c进行第二阶段反应。Basically the same as Example 4, the difference is only that: in the preparation process of the polyurethane prepolymer, 15kg BASF MDI-MI and 15kg BASF modified MDI103c were added to carry out the first-stage reaction, and then 35kg BASF MDI-MI and 35kg BASF were added. BASF modified MDI103c for the second stage reaction.
测得性能如下：粘度22000mpa.s(25℃)，12100mpa.s(50℃)，固含量88.9％，表干时间2小时，实干时间6小时，7天拉伸强度3.1MPa，断裂伸长率678％，撕裂强度18N/mm；The measured properties are as follows: viscosity 22000mpa.s (25°C), 12100mpa.s (50°C), solid content 88.9%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 3.1MPa, elongation at break 678%, tear strength 18N/mm;
50℃基面机械喷涂施工后情况如下：一次厚涂1.5mm不流淌。The situation after mechanical spraying on the base surface at 50°C is as follows: a thick coating of 1.5mm does not flow.
对比例1Comparative Example 1
基本同实施例4，其区别仅在于：将实施例1的仲胺化合物替换为市售常用的扩链剂clearlink 1000 4,4’双仲丁氨基二环己基甲烷。Basically the same as Example 4, the difference is only that: the secondary amine compound of Example 1 is replaced by the commercially available chain extender clearlink 1000 4,4'-bis-sec-butylaminodicyclohexylmethane.
测得性能如下：粘度35000mpa.s(25℃)，21900mpa.s(50℃)，固含量88.8％，表干时间2小时，实干时间6小时，7天拉伸强度1.1MPa，断裂伸长率546％，撕裂强度15N/mm；50℃基面机械喷涂施工后情况如下：一次厚涂1mm流淌。The measured properties are as follows: viscosity 35000mpa.s (25℃), 21900mpa.s (50℃), solid content 88.8%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 1.1MPa, elongation at break 546%, tear strength 15N/mm; 50°C base surface after mechanical spraying construction is as follows: a thick coating of 1mm flows.
对比例2Comparative Example 2
基本同实施例4，其区别仅在于：将实施例1的仲胺化合物替换为市售常用的扩链剂亚甲基双邻氯苯胺(moca)。It is basically the same as Example 4, except that the secondary amine compound in Example 1 is replaced with a commercially available chain extender, methylenebis-o-chloroaniline (moca).
测得性能如下：粘度45370mpa.s(25℃)，28900mpa.s(50℃)，固含量88.9％，表干时间2小时，实干时间6小时，7天拉伸强度1.8MPa，断裂伸长率457％，撕裂强度13N/mm；The measured properties are as follows: viscosity 45370mpa.s (25℃), 28900mpa.s (50℃), solid content 88.9%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 1.8MPa, elongation at break 457%, tear strength 13N/mm;
50℃基面机械喷涂施工后情况如下：一次厚涂1mm流淌。The situation after mechanical spraying on the base surface at 50°C is as follows: a thick coating of 1mm flows.
对比例3Comparative Example 3
基本同实施例4，其区别仅在于：所述聚氨酯预聚体通过使多元醇、实施例1的仲胺化合物和全部异氰酸酯混合一起在80±2℃下反应制成。It is basically the same as Example 4, except that the polyurethane prepolymer is prepared by mixing the polyol, the secondary amine compound of Example 1 and all the isocyanates and reacting together at 80±2°C.
测得性能如下：粘度34600mpa.s(25℃)，17600mpa.s(50℃)，固含量89％，表干时间2小时，实干时间6小时，7天拉伸强度2.3MPa，断裂伸长率478％，撕裂强度15N/mm；The measured properties are as follows: viscosity 34600mpa.s (25°C), 17600mpa.s (50°C), solid content 89%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 2.3MPa, elongation at break 478%, tear strength 15N/mm;
50℃基面机械喷涂施工后情况如下：一次厚涂1mm流淌。The situation after mechanical spraying on the base surface at 50°C is as follows: a thick coating of 1mm flows.
对比例4Comparative Example 4
基本同实施例4，其区别仅在于：所述聚氨酯预聚体通过使多元醇和全部异氰酸酯在80±2℃下反应2h后，再与实施例1的仲胺化合物反应1h，制成。Basically the same as Example 4, the only difference is that the polyurethane prepolymer is prepared by reacting polyol and all isocyanates at 80±2° C. for 2 hours, and then reacting with the secondary amine compound of Example 1 for 1 hour.
测得性能如下：粘度44900mpa.s(25℃)，22300mpa.s(50℃)，固含量89％，表干时间2小时，实干时间6小时，7天拉伸强度2.1MPa，断裂伸长率786％，撕裂强度16N/mm；The measured properties are as follows: viscosity 44900mpa.s (25℃), 22300mpa.s (50℃), solid content 89%, surface dry time 2 hours, solid dry time 6 hours, 7 days tensile strength 2.1MPa, elongation at break 786%, tear strength 16N/mm;
50℃基面机械喷涂施工后情况如下：一次厚涂1mm流淌。The situation after mechanical spraying on the base surface at 50°C is as follows: a thick coating of 1mm flows.
上述实施例只为说明本发明的技术构思及特点，其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围，凡根据本发明精神实质所作的等效变化或修饰，都应涵盖在本发明的保护范围之内。The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and their purpose is to enable those who are familiar with the technology to understand the content of the present invention and implement it accordingly, and cannot limit the scope of protection of the present invention. Equivalent changes or modifications made in the spirit and spirit should all be included within the protection scope of the present invention.

Claims (20)

  1. 一种聚氨酯防水涂料，所述聚氨酯防水涂料包括聚氨酯预聚体和助剂，其特征在于，所述聚氨酯预聚体的原料包括多元醇、多异氰酸酯和仲胺化合物；所述仲胺化合物为选自式(Ⅰ)所示化合物中的一种或多种的组合：A polyurethane waterproof coating, the polyurethane waterproof coating comprises a polyurethane prepolymer and an auxiliary, and is characterized in that the raw materials of the polyurethane prepolymer include polyol, polyisocyanate and secondary amine compound; the secondary amine compound is selected from A combination of one or more of the compounds represented by formula (I):
    Figure PCTCN2021102729-appb-100001
    Figure PCTCN2021102729-appb-100001
    其中，R 1为支链亚烷基； Wherein, R 1 is branched alkylene;
    R 2为H或C 1-10烷基，或为被选自C 1-6烷基、C 1-6烷氧基中的一个或多个所取代的C 1-10烷基或苯基； R 2 is H or C 1-10 alkyl, or C 1-10 alkyl or phenyl substituted by one or more selected from C 1-6 alkyl, C 1-6 alkoxy;
    所述聚氨酯预聚体通过使多元醇、仲胺化合物和部分异氰酸酯混合反应后再加入剩余异氰酸酯再次反应而制成；其中，控制所述多元醇、所述仲胺化合物和所述部分异氰酸酯的混合反应的温度小于等于60℃，加入剩余异氰酸酯后的反应温度为75-85℃，所述多元醇、所述异氰酸酯和所述仲胺化合物的投料质量比为1∶0.2-0.5∶0.05-0.15，所述多元醇由二元醇和三元醇构成，所述二元醇与所述三元醇的投料质量比为1∶0.1-1，控制所述聚氨酯预聚体的NCO的质量含量为2-6％；The polyurethane prepolymer is prepared by mixing and reacting the polyol, the secondary amine compound and the partial isocyanate, and then adding the remaining isocyanate to react again; wherein, the mixing of the polyol, the secondary amine compound and the partial isocyanate is controlled The temperature of the reaction is less than or equal to 60 ° C, the reaction temperature after adding the remaining isocyanate is 75-85 ° C, and the mass ratio of the polyol, the isocyanate and the secondary amine compound is 1: 0.2-0.5: 0.05-0.15, 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 the mass content of NCO controlling the polyurethane prepolymer is 2- 6%;
    所述助剂包括催化剂，所述催化剂由投料质量比为1∶0.4-0.8∶0.2-0.6的二月桂酸二丁基锡、五甲基二亚丙基三胺和异辛酸锌构成；The auxiliary agent includes a catalyst, and the catalyst is composed of dibutyltin dilaurate, pentamethyldipropylenetriamine and zinc isooctanoate with a mass ratio of 1:0.4-0.8:0.2-0.6;
    所述助剂还包括填料、增塑剂、分散剂、活性稀释剂、溶剂、触变剂、除水剂和消泡剂；以质量份数计，所述聚氨酯防水涂料中，聚氨酯预聚体20-50份、填料20-50份、增塑剂5-30份、分散剂0.1-1份、活性稀释剂0.3-2份、溶剂0.5-15份、触变剂0.1-2份、除水剂0.1-1份、催化剂0.05-1份和消泡剂0.1-1份。The auxiliary agents also include fillers, plasticizers, dispersants, reactive diluents, solvents, thixotropic agents, dewatering agents and defoaming agents; in parts by mass, in the polyurethane waterproof coating, the polyurethane prepolymer 20-50 parts, filler 20-50 parts, plasticizer 5-30 parts, dispersant 0.1-1 part, reactive diluent 0.3-2 parts, solvent 0.5-15 parts, thixotropic agent 0.1-2 parts, water removal 0.1-1 part of catalyst, 0.05-1 part of catalyst and 0.1-1 part of defoamer.
  2. 一种聚氨酯防水涂料，所述聚氨酯防水涂料包括聚氨酯预聚体和助剂，其特征在于，所述聚氨酯预聚体的原料包括多元醇、异氰酸酯和仲胺化合物，所述仲胺化合物为选自式(Ⅰ)所示化合物中的一种或多种的组合：A polyurethane waterproof coating, the polyurethane waterproof coating includes a polyurethane prepolymer and an auxiliary, and is characterized in that, the raw materials of the polyurethane prepolymer include polyol, isocyanate and secondary amine compound, and the secondary amine compound is selected from the group consisting of A combination of one or more of the compounds represented by formula (I):
    Figure PCTCN2021102729-appb-100002
    Figure PCTCN2021102729-appb-100002
    其中，R 1为支链亚烷基； Wherein, R 1 is branched alkylene;
    R 2为H或C 1-10烷基，或为被选自C 1-6烷基、C 1-6烷氧基中的一个或多个所取代的C 1-10烷基或苯基； R 2 is H or C 1-10 alkyl, or C 1-10 alkyl or phenyl substituted by one or more selected from C 1-6 alkyl, C 1-6 alkoxy;
    所述聚氨酯预聚体通过使多元醇、仲胺化合物和部分异氰酸酯混合反应后再加入剩余异氰酸酯再次反应而制成。The polyurethane prepolymer is prepared by mixing and reacting polyol, secondary amine compound and part of isocyanate, and then adding the remaining isocyanate to react again.
  3. 根据权利要求1或2所述的聚氨酯防水涂料，其特征在于，R 1为C 3-10支链亚烷基。 The polyurethane waterproof coating according to claim 1 or 2, wherein R 1 is a C 3-10 branched alkylene group.
  4. 根据权利要求1或2所述的聚氨酯防水涂料，其特征在于，R 2为H、甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、甲氧基甲基、甲氧基乙基、甲氧基丙基、甲氧基异丙基、甲氧基丁基、甲氧基异丁基、甲氧基戊基、乙氧基甲基、乙氧基乙基、乙氧基丙基、乙氧基异丙基、乙氧基丁基、乙氧基异丁基、乙氧基戊基、甲基苯基、乙基苯基、甲氧基苯基、乙氧基苯基或苯基。 The polyurethane waterproof coating according to claim 1 or 2, wherein R 2 is 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, ethyl oxyphenyl or phenyl.
  5. 根据权利要求1或2所述的聚氨酯防水涂料，其特征在于，所述仲胺化合物为选自下式结构所示化合物中的一种或多种的组合：The polyurethane waterproof coating according to claim 1 or 2, wherein the secondary amine compound is a combination of one or more selected from the compounds represented by the following formula:
    Figure PCTCN2021102729-appb-100003
    Figure PCTCN2021102729-appb-100003
    Figure PCTCN2021102729-appb-100004
    Figure PCTCN2021102729-appb-100004
  6. 根据权利要求2所述的聚氨酯防水涂料，其特征在于，所述多元醇、所述异氰酸酯和所述仲胺化合物的投料质量比为1∶0.2-0.5∶0.05-0.15。The polyurethane waterproof coating according to claim 2, wherein the mass ratio of the polyol, the isocyanate and the secondary amine compound is 1:0.2-0.5:0.05-0.15.
  7. 根据权利要求2所述的聚氨酯防水涂料，其特征在于，所述聚氨酯预聚体的NCO的质量含量为2-6％。The polyurethane waterproof coating according to claim 2, wherein the mass content of NCO of the polyurethane prepolymer is 2-6%.
  8. 根据权利要求2所述的聚氨酯防水涂料，其特征在于，所述多元醇由二元醇和三元醇构成，所述二元醇与所述三元醇的投料质量比为 1∶0.1-1.Polyurethane waterproof coating according to claim 2, is characterized in that, described polyhydric alcohol is made up of dihydric alcohol and trihydric alcohol, and the feeding mass ratio of described dihydric alcohol and described trihydric alcohol is 1: 0.1-1.
  9. 根据权利要求1或2所述的聚氨酯防水涂料，其特征在于，所述异氰酸酯为多异氰酸酯，所述多异氰酸酯为选自甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、改性二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯和六亚甲基二异氰酸酯中至少两种的组合。The polyurethane waterproof coating according to claim 1 or 2, wherein the isocyanate is a polyisocyanate, and the polyisocyanate is selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, modified A combination of at least two of diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.
  10. 根据权利要求2所述的聚氨酯防水涂料，其特征在于，制备所述聚氨酯预聚体的过程中，控制所述多元醇、所述仲胺化合物和所述部分异氰酸酯的混合反应的温度小于等于60℃，加入剩余异氰酸酯后的反应温度为75-85℃。The polyurethane waterproof coating according to claim 2, wherein, in the process of preparing the polyurethane prepolymer, the temperature for controlling the mixing reaction of the polyol, the secondary amine compound and the partial isocyanate is less than or equal to 60 °C, and the reaction temperature after adding the remaining isocyanate is 75-85 °C.
  11. 根据权利要求10所述的聚氨酯防水涂料，其特征在于，以质量百分含量计，所述部分异氰酸酯占总的异氰酸酯的20-50％。The polyurethane waterproof coating according to claim 10, wherein, in terms of mass percentage, the partial isocyanate accounts for 20-50% of the total isocyanate.
  12. 根据权利要求11所述的聚氨酯防水涂料，其特征在于，以质量百分含量计，所述部分异氰酸酯占总的异氰酸酯的20-40％。The polyurethane waterproof coating according to claim 11, wherein, in terms of mass percentage, the partial isocyanate accounts for 20-40% of the total isocyanate.
  13. 根据权利要求2所述的聚氨酯防水涂料，其特征在于，所述助剂包括催化剂，所述催化剂由投料质量比为1∶0.4-0.8∶0.2-0.6的二月桂酸二丁基锡、五甲基二亚丙基三胺和异辛酸锌构成。The polyurethane waterproof coating according to claim 2, wherein the auxiliary agent comprises a catalyst, and the catalyst is composed of dibutyl tin dilaurate, pentamethyl dilaurate and pentamethyl dilaurate in a mass ratio of 1: 0.4-0.8: 0.2-0.6. It consists of propylene triamine and zinc isooctanoate.
  14. 根据权利要求13所述的聚氨酯防水涂料，其特征在于，所述助剂还包括填料、增塑剂、分散剂、活性稀释剂、溶剂、触变剂、除水剂和消泡剂；以质量份数计，所述聚氨酯防水涂料中，聚氨酯预聚体20-50份、填料20-50份、增塑剂5-30份、分散剂0.1-1份、活性稀释剂0.3-2份、溶剂0.5-15份、触变剂0.1-2份、除水剂0.1-1份、催化剂0.05-1份和消泡剂0.1-1份。The polyurethane waterproof coating according to claim 13, wherein the auxiliary agent further comprises fillers, plasticizers, dispersants, reactive diluents, solvents, thixotropic agents, dewatering agents and defoaming agents; In terms of parts, in the polyurethane waterproof coating, 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 reactive diluent, solvent 0.5-15 parts, 0.1-2 parts of thixotropic agent, 0.1-1 part of water scavenger, 0.05-1 part of catalyst and 0.1-1 part of defoamer.
  15. 根据权利要求1或2所述的聚氨酯防水涂料，其特征在于，所述式(Ⅰ)所示化合物的制备方法包括：The polyurethane waterproof coating according to claim 1 or 2, wherein the preparation method of the compound represented by the formula (I) comprises:
    (a)使苯酚与醛类化合物混合，升温反应；(a) make phenol and aldehyde compound mix, temperature rise reaction;
    (b)向步骤(a)反应后的反应液中加入H 2N-R 1-NH 2，混合，升温反应，然后真空脱水和/或升温脱水，控制水分含量500ppm以下，直到得到透明粘稠状液体，制成所述式(Ⅰ)所示化合物；其中，R 1同权利要求1或2。 (b) adding H 2 NR 1 -NH 2 to the reaction solution after the reaction in step (a), mixing, heating up the reaction, then vacuum dehydration and/or dehydration at elevated temperature, and controlling the moisture content to be less than 500 ppm until a transparent viscous liquid is obtained , to prepare the compound represented by the formula (I); wherein, R 1 is the same as claim 1 or 2.
  16. 根据权利要求15所述的聚氨酯防水涂料，其特征在于，所述苯酚、所述醛类化合物和所述H 2N-R 1-NH 2的投料摩尔比为1∶0.5-2∶0.5-1。 The polyurethane waterproof coating according to claim 15, wherein the molar ratio of the phenol, the aldehyde compound and the H 2 NR 1 -NH 2 is 1:0.5-2:0.5-1.
  17. 根据权利要求15所述的聚氨酯防水涂料，其特征在于，所述苯酚与所述醛类化合物的反应温度为50-80℃，加入H 2N-R 1-NH 2之后的反应温度为100-150℃。 The polyurethane waterproof coating according to claim 15, wherein the reaction temperature of the phenol and the aldehyde compound is 50-80°C, and the reaction temperature after adding H 2 NR 1 -NH 2 is 100-150° C. .
  18. 根据权利要求15所述的聚氨酯防水涂料，其特征在于，使所述苯酚与所述醛类化合物的反应在碱土金属镁型催化剂存在下进行，所述碱土金属镁型催化剂由投料摩尔比为1∶0.8-1.2的氢氧化镁和氧化镁构成。The polyurethane waterproof coating according to claim 15, wherein the reaction of the phenol and the aldehyde compound is carried out in the presence of an alkaline earth metal magnesium type catalyst, and the alkaline earth metal magnesium type catalyst is charged with a molar ratio of 1 : 0.8-1.2 magnesium hydroxide and magnesium oxide composition.
  19. 一种权利要求1-18中任一项所述的聚氨酯防水涂料的制备方法，其特征在于，所述制备方法包括如下步骤：A preparation method of the polyurethane waterproof coating according to any one of claims 1-18, wherein the preparation method comprises the steps:
    (1)制备聚氨酯预聚体(1) Preparation of polyurethane prepolymer
    将多元醇与式(Ⅰ)所示的仲胺化合物混合，加入部分异氰酸酯，在温度为60℃以下的条件下进行第一阶段反应；然后加入剩余异氰酸酯，升温至75-85℃，进行第二阶段反应，制成聚氨酯预聚体；其中，所述第一阶段反应、所述第二阶段反应分别在保护气体保护下进行；Mix the polyol with the secondary amine compound represented by the formula (I), add part of the isocyanate, and carry out the first-stage reaction under the condition that the temperature is below 60 ° C; then add the remaining isocyanate, heat up to 75-85 ° C, carry out the second stage staged reaction to make polyurethane prepolymer; wherein, the first stage reaction and the second stage reaction are carried out under the protection of protective gas;
    (2)将步骤(1)制成的聚氨酯预聚体与助剂混合，制成所述聚氨酯防水涂料。(2) Mixing the polyurethane prepolymer prepared in step (1) with an auxiliary agent to prepare the polyurethane waterproof coating.
  20. 一种权利要求1-18中任一项所述的聚氨酯防水涂料在温度达到50℃以上的基层上进行喷涂施工的用途，所述基层为倾斜设置和/或竖直设置。A use of the polyurethane waterproof coating according to any one of claims 1 to 18 for spraying construction on a base layer whose temperature reaches above 50°C, and the base layer is inclined and/or vertical.
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Publication number Priority date Publication date Assignee Title
CN112898889B (en) * 2021-01-26 2022-04-01 江苏凯伦建材股份有限公司 Polyurethane waterproof coating and application thereof
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

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1154981A (en) * 1995-12-13 1997-07-23 国际壳牌研究有限公司 Mannich base solidification agent
CN108699220A (en) * 2016-02-15 2018-10-23 Sika技术股份公司 The curing agent of low emission composition epoxy resin
CN109321122A (en) * 2018-08-29 2019-02-12 江苏凯伦建材股份有限公司 A kind of solvent-free anti-sag polyurethane water-proof paint of quick-dry type and preparation method thereof
CN110790880A (en) * 2019-11-15 2020-02-14 万华化学集团股份有限公司 Preparation method of TDI tripolymer, TDI tripolymer containing solvent and application thereof
CN110791165A (en) * 2019-11-28 2020-02-14 河南东方雨虹建筑材料有限公司 Single-component anti-sagging exposed modified polyurethane waterproof coating and preparation method thereof
CN112898889A (en) * 2021-01-26 2021-06-04 江苏凯伦建材股份有限公司 Polyurethane waterproof coating and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2644632A1 (en) * 2012-03-29 2013-10-02 Huntsman International Llc Isocyanate-based prepolymer
CN102993930A (en) * 2012-09-29 2013-03-27 北京东方雨虹防水技术股份有限公司 Highly-heat-resistant spray polyurea elastic coating and preparation method for same
KR101867552B1 (en) * 2016-04-29 2018-07-17 공주대학교 산학협력단 Preperation method of water-dispersible polyurethane prepolymer and polyurethane coating layer
CN107118179B (en) * 2017-05-05 2020-09-22 北京东方雨虹防水技术股份有限公司 Imine compound, preparation method and application thereof, and single-component polyurethane waterproof coating
CN107474713A (en) * 2017-08-24 2017-12-15 江苏凯伦建材股份有限公司 A kind of polyurea waterproof coating material of one pack system anti-sag high-strength weather-resistant half and preparation method thereof
CN111253849A (en) * 2019-12-17 2020-06-09 江苏凯伦建材股份有限公司 Single-component solvent-free anti-sagging polyurethane waterproof coating, production system and production method thereof
CN111363470A (en) * 2020-05-08 2020-07-03 四川省宏源防水工程有限公司 Anti-sagging facade construction type single-component polyurethane waterproof coating and preparation and construction methods thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1154981A (en) * 1995-12-13 1997-07-23 国际壳牌研究有限公司 Mannich base solidification agent
CN108699220A (en) * 2016-02-15 2018-10-23 Sika技术股份公司 The curing agent of low emission composition epoxy resin
CN109321122A (en) * 2018-08-29 2019-02-12 江苏凯伦建材股份有限公司 A kind of solvent-free anti-sag polyurethane water-proof paint of quick-dry type and preparation method thereof
CN110790880A (en) * 2019-11-15 2020-02-14 万华化学集团股份有限公司 Preparation method of TDI tripolymer, TDI tripolymer containing solvent and application thereof
CN110791165A (en) * 2019-11-28 2020-02-14 河南东方雨虹建筑材料有限公司 Single-component anti-sagging exposed modified polyurethane waterproof coating and preparation method thereof
CN112898889A (en) * 2021-01-26 2021-06-04 江苏凯伦建材股份有限公司 Polyurethane waterproof coating and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116042072A (en) * 2023-01-13 2023-05-02 上海固密特新材料科技有限公司 Flexible weather-resistant epoxy coating and application thereof
CN116042072B (en) * 2023-01-13 2024-04-26 上海固密特新材料科技有限公司 Flexible weather-resistant epoxy coating and application thereof

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