WO2022148082A1 - 一种光固化双组份聚脲防水涂料及其制备方法 - Google Patents

一种光固化双组份聚脲防水涂料及其制备方法 Download PDF

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WO2022148082A1
WO2022148082A1 PCT/CN2021/123453 CN2021123453W WO2022148082A1 WO 2022148082 A1 WO2022148082 A1 WO 2022148082A1 CN 2021123453 W CN2021123453 W CN 2021123453W WO 2022148082 A1 WO2022148082 A1 WO 2022148082A1
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component
polyurea
polyurea prepolymer
hydroxyl
prepolymer
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PCT/CN2021/123453
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English (en)
French (fr)
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贺小钢
朱洋洋
高凡
李忠人
谭宇昂
周围
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江苏凯伦建材股份有限公司
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Publication of WO2022148082A1 publication Critical patent/WO2022148082A1/zh

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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
    • C09D175/02—Polyureas
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary amino 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • 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
    • C08G18/6685—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 C08G18/3225 or polyamines of C08G18/38

Definitions

  • the invention belongs to the field of waterproof coatings, in particular to a light-cured two-component polyurea waterproof coating and a preparation method thereof.
  • Polyurea coating is a kind of reactive and pollution-free high-performance coating developed at home and abroad this year. In recent years, a polyaspartate polyurea coating has been developed. The introduction of polyaspartate into the polyurea coating makes the polyaspartate polyurea coating have excellent weather resistance, good leveling, etc. advantage.
  • a modified polyaspartate polyurea coating and its preparation method are disclosed.
  • the polyurea coating is composed of component A and component B, wherein, in parts by weight, component A is composed of It is an isocyanate and/or a polymer of isocyanate; the composition of component B is 20-75 parts of silicone and epoxy double-modified polyaspartate resin, 5-35 parts of filler, 0.1-5 parts of pigment, 0.5 part of ⁇ 10 parts of adjuvant and 5 to 30 parts of solvent.
  • the polyurea coating improves the low temperature flexibility, bonding strength, weather resistance and mechanical properties of the polyurea coating.
  • the curing and cross-linking need to depend on the ambient temperature, the strength of deep curing takes time, and the construction efficiency is not high.
  • the present invention provides a light-cured two-component polyurea waterproof coating and a preparation method thereof, which can achieve rapid deep drying and curing into a film after ultraviolet light irradiation, and excellent Excellent adhesion and self-healing properties.
  • a light-curing two-component polyurea waterproof coating is composed of A component and B component, and the raw material formula of the A component includes a polyurea prepolymer and an acrylic modified polyurea prepolymer, wherein the said The polyurea prepolymer is prepared by the reaction of isocyanate and sterically hindered secondary amine;
  • the raw material formula of the B component includes the following components:
  • the sterically hindered secondary amine and the amine chain extender are independently selected from one or more combinations of the aspartate sterically hindered secondary amine compounds shown in formula I:
  • X is an alkyl group with 1-3 carbon atoms
  • R 1 , R 2 , R 3 , and R 4 are independently selected from linear or branched alkyl groups with 2-8 carbon atoms, —R 5 Ph or a cyclic alkyl group having 6 to 10 carbon atoms
  • R 5 is an alkyl group having 1 to 4 carbon atoms.
  • X is CH 2
  • R 1 , R 2 , R 3 , and R 4 are independently CH 2 CH 3 , —R 5 Ph or 6-carbon atoms.
  • a cyclic alkyl group of 10 is an alkyl group having 1 to 4 carbon atoms.
  • the acrylic modified polyurea prepolymer is prepared by reacting a hydroxyl-containing acrylate and/or a hydroxyl-containing acrylic resin with the polyurea prepolymer, wherein the The hydroxyl-containing acrylate is one or more of hydroxyethyl acrylate and hydroxyethyl methacrylate, and the hydroxyl-containing acrylic resin is a hydroxyl acrylic resin.
  • the hydroxy acrylic resin is hydroxy acrylic resin HAR863, hydroxy acrylic resin HAR864, hydroxy acrylic resin HAR865, hydroxy acrylic resin HAR867, hydroxy acrylic resin HAR 869, hydroxy acrylic resin HAR869, One or more of resin HAR887, hydroxy acrylic resin HAR960 and hydroxy acrylic resin HAR970.
  • the mass ratio between the polyurea prepolymer and the hydroxyl-containing acrylate and/or the hydroxyl-containing acrylic resin is 0.1-1:1.
  • acrylic acid through the modification of acrylic acid, the introduction of acrylic acid enables the double bond of acrylic acid to realize cross-linking curing reaction under the action of photoinitiator, and the acrylic acid is grafted to the main chain of polyurea to realize end capping and provide cross-linking points.
  • the isocyanate is one or more of MDI, TDI, IPDI, HDI, hydrogenated MDI, and XDI.
  • the isocyanate is MDI.
  • the use of MDI is more conducive to obtaining materials with excellent tensile strength and elongation.
  • the mass ratio of the sterically hindered secondary amine to the isocyanate is 1-3:1.
  • the mass ratio of the polyurea prepolymer and the acrylic modified polyurea prepolymer is 0.25-5:1.
  • the mass ratio of the polyurea prepolymer and the acrylic modified polyurea prepolymer is 0.8-1.2:1.
  • the photoinitiator is fluorinated diphenyltitanocene, bis(pentafluorophenyl)titanocene, benzophenone derivatives, thioxanthone derivatives, alkylarylketone derivatives One or more of benzil derivatives and benzil derivatives.
  • the photoinitiator is Tianjin Jiuri New Materials JRCure-1055, JRCure-1065, JRCure-1103, JRCure-1104, JRCure-1107, JRCure-1108, JRCure-1110, JRCure- One or more of 1112, JRCure-1113, JRCure-1114, and JRCure-1116.
  • the amino-terminated polyether is one or more of primary amino polyether and secondary amino polyether.
  • the primary amino polyether is one or more of Huntsman's D230, D400, D2000, D4000, T403, T3000, and T5000
  • the secondary amino polyether is Huntsman One or more of SD231, SD401, and SD2001 of Siman.
  • the defoamer is one or more of a physical defoamer and a chemical defoamer.
  • the physical defoamer is a polysiloxane defoamer and/or a silicone-based defoamer
  • the chemical defoamer is calcium oxide, magnesium oxide, calcium hydroxide, One or a combination of oxazolidine-based latent curing agents and ketimine-based latent curing agents.
  • the antioxidant is 2,6-tert-butyl-4-methylphenol, bis(3,5-tert-butyl-4-hydroxyphenyl) sulfide, tetrakis A combination of one or more of [ ⁇ -(3,5-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol esters.
  • the plasticizer is at least one of naphthenic oil, chlorinated paraffin, DINP, DIDP, DOTP, vegetable oil and the like.
  • the mass ratio of the A component and the B component is 1:0.8-1.2.
  • the polyurea prepolymer and the acrylic modified polyurea prepolymer in the A component can first react with the amino material in the B component to form an initial molecular cross-linking structure , and then the carbon-carbon double bond in the acrylic acid can be rapidly dried and cured into a film after being irradiated by ultraviolet light, and quickly cross-linked and cured to achieve the final strength, as well as excellent adhesion and self-healing performance.
  • the preparation method of the above-mentioned light-cured two-component polyurea waterproof coating comprises the following steps:
  • the sterically hindered secondary amine is dehydrated to a moisture content of less than 300 ppm at 100-130 °C, isocyanate is added, and the reaction is carried out at 70-100 °C to obtain a polyurea prepolymer;
  • step (1) The polyurea prepolymer prepared in step (1), the hydroxyl-containing acrylate and/or the hydroxyl-containing acrylic resin, and the polymerization inhibitor are mixed, and the reaction is carried out at 70 to 100° C. to obtain an acrylic modified polyurea prepolymer. aggregate;
  • the mass ratio of the sterically hindered secondary amine to isocyanate is 0.2-3:1.
  • the mass ratio of the sterically hindered secondary amine to the isocyanate is 1-3:1.
  • step (1) is as follows: dehydrate the hindered secondary amine to a moisture content of less than 300 ppm at 100-130° C., drop isocyanate, and react at 70-100° C. for 2-4 hours , the mass fraction of NCO was sampled and tested to reach the design value of 1-5%, the reaction was terminated, and the polyurea prepolymer was obtained.
  • step (2) the feeding ratio of the polyurea prepolymer, the hydroxyl-containing acrylate and/or the hydroxyl-containing acrylic resin, and the polymerization inhibitor is 0.1-1:1:0.005-0.015.
  • step (2) is: mixing polyurea prepolymer, hydroxyl-containing acrylate and/or hydroxyl-containing acrylic resin, and polymerization inhibitor at 70-100° C. The reaction is carried out for 4-6 hours, the mass fraction of NCO is determined to reach the designed value, the reaction is terminated, and the acrylic acid modified polyurea prepolymer is obtained.
  • the present invention has the following advantages compared with the prior art:
  • polyurea waterproof coating of the present invention aspartic acid ester compounds are introduced into both the A component and the B component, together with the use of a photoinitiator, so that the prepared polyurea waterproof coating can achieve rapid Deep drying and curing into a film, it has good weather resistance, and acrylic modification is introduced, so that the polyurea waterproof coating has both the flexibility of polyurethane and the hardness of acrylic.
  • the polyurea waterproof coating of the present invention also has excellent adhesion, excellent self-healing and self-healing performance, and long open time.
  • the polyurea waterproof coating of the invention has a solid content of 100%, is safe and environmentally friendly, has no irritating odor, has low construction viscosity, can realize spray construction, can be used for low pressure spraying machine construction, and has fast material gelation speed.
  • the sterically hindered secondary amine has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as amine chain extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the isocyanate is MDI-MIPS.
  • the amino-terminated polyether is Huntsman SD2001.
  • the amine chain extender has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as Amine Chain Extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the photoinitiator was JRCURE-1110.
  • the defoamer is polysiloxane defoamer 8110.
  • the antioxidant was 2,6-tert-butyl-4-methylphenol.
  • the light-curing two-component polyurea waterproof coating is prepared by the following method:
  • step (1) 250kg of polyurea prepolymer obtained in step (1), 500kg of hydroxyl-containing acrylate HAR864, and 5kg of 705 polymerization inhibitor were mixed, and the reaction was carried out at 80 ° C to obtain 755kg of acrylic acid modified polyurea prepolymer;
  • the prepolymer is mixed to obtain 500kg of component A;
  • the mass ratio of component A and component B is 1:1. After stirring and mixing, it is coated on the construction base, and then uniformly irradiated with 340nm ultraviolet light to form a film.
  • the difference between the light-cured two-component polyurea waterproof coating provided in this example and Example 1 is that in the A component, the feeding mass ratio of the polyurea prepolymer and the acrylic modified polyurea prepolymer is different.
  • amine chain extender No. 1 JH334 of Junhe Chemical (Shanghai) Co., Ltd., referred to as amine chain extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the isocyanate is MDI-MIPS.
  • the amino-terminated polyether is Huntsman SD2001.
  • the amine chain extender has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as Amine Chain Extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the photoinitiator was JRCURE-1110.
  • the defoamer is polysiloxane defoamer 8110.
  • the antioxidant was 2,6-tert-butyl-4-methylphenol.
  • the plasticizer is DINP.
  • the light-curing two-component polyurea waterproof coating is prepared by the following method:
  • step (1) 250kg of polyurea prepolymer obtained in step (1), 500kg of hydroxyl-containing acrylate HAR864, and 5kg of 705 polymerization inhibitor were mixed, and the reaction was carried out at 80 ° C to obtain 755kg of acrylic acid modified polyurea prepolymer;
  • the mass ratio of component A and component B is 1:1. After stirring and mixing, it is coated on the construction base, and then uniformly irradiated with 340nm ultraviolet light to form a film.
  • the difference between the light-cured two-component polyurea waterproof coating provided in this example and Example 1 is that in the A component, the feeding mass ratio of the polyurea prepolymer and the acrylic modified polyurea prepolymer is different.
  • the sterically hindered secondary amine has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as amine chain extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the isocyanate is MDI-MIPS.
  • the amino-terminated polyether is Huntsman SD2001.
  • the amine chain extender has the following structure, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as Amine Chain Extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the photoinitiator was JRCURE-1110.
  • the defoamer is polysiloxane defoamer 8110.
  • the antioxidant was 2,6-tert-butyl-4-methylphenol.
  • the plasticizer is DINP.
  • the light-curing two-component polyurea waterproof coating is prepared by the following method:
  • step (1) 250kg of polyurea prepolymer obtained in step (1), 500kg of hydroxyl-containing acrylate HAR864, and 5kg of 705 polymerization inhibitor were mixed, and the reaction was carried out at 80 ° C to obtain 755kg of acrylic acid modified polyurea prepolymer;
  • the mass ratio of component A and component B is 1:1. After stirring and mixing, it is coated on the construction base, and then uniformly irradiated with 340nm ultraviolet light to form a film.
  • the light-curing two-component polyurea waterproof coating provided in this example is different from Example 1 in that no polyurea prepolymer is added to the A component.
  • the sterically hindered secondary amine has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as amine chain extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the isocyanate is MDI-MIPS.
  • the amino-terminated polyether is Huntsman SD2001.
  • the amine chain extender has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as Amine Chain Extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the photoinitiator was JRCURE-1110.
  • the defoamer is polysiloxane defoamer 8110.
  • the antioxidant was 2,6-tert-butyl-4-methylphenol.
  • the plasticizer is DINP.
  • the light-curing two-component polyurea waterproof coating is prepared by the following method:
  • the polymers are mixed to obtain 500kg of A component.
  • the mass ratio of component A and component B is 1:1. After stirring and mixing, it is coated on the construction base, and then uniformly irradiated with 340nm ultraviolet light to form a film.
  • the two-component polyurea waterproof coating provided in this example is different from Example 1 in that no photoinitiator is added.
  • the sterically hindered secondary amine has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as amine chain extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the isocyanate is MDI-MIPS.
  • the amino-terminated polyether is Huntsman SD2001.
  • the amine chain extender has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as Amine Chain Extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the defoamer is polysiloxane defoamer 8110.
  • the antioxidant was 2,6-tert-butyl-4-methylphenol.
  • the plasticizer is DINP.
  • the two-component polyurea waterproof coating is prepared by the following method:
  • Prepolymers are mixed to obtain 500kg of A component
  • the mass ratio of component A and component B is 1:1. After stirring and mixing, it is coated on the construction base, and then uniformly irradiated with 340nm ultraviolet light to form a film.
  • the two-component polyurea waterproof coating provided in this example is different from Example 1 in that the amine chain extender adopts unilink4200.
  • the hindered secondary amine is unilink4200.
  • the isocyanate is MDI-MIPS.
  • the amino-terminated polyether is Huntsman SD2001.
  • Amine chain extender is unilink4200.
  • the photoinitiator was JRCURE-1110.
  • the defoamer is polysiloxane defoamer 8110.
  • the antioxidant was 2,6-tert-butyl-4-methylphenol.
  • the plasticizer is DINP.
  • the light-curing two-component polyurea waterproof coating is prepared by the following method:
  • the prepolymers were mixed to obtain 500kg of A component.
  • the mass ratio of component A and component B is 1:1. After stirring and mixing, it is coated on the construction base, and then uniformly irradiated with 340nm ultraviolet light to form a film.
  • the two-component polyurea waterproof coating provided in this example is different from Example 1 in that the A component adopts isocyanate as TDI.
  • the sterically hindered secondary amine has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as amine chain extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the isocyanate is TDI.
  • the amino-terminated polyether is Huntsman SD2001.
  • the amine chain extender has the following structural formula, specifically JH334 from Junhe Chemical (Shanghai) Co., Ltd., referred to as Amine Chain Extender No. 1:
  • X is CH 2
  • R 1 , R 2 , R 3 and R 4 are respectively CH 2 CH 3 .
  • the photoinitiator was JRCURE-1110.
  • the defoamer is polysiloxane defoamer 8110.
  • the antioxidant was 2,6-tert-butyl-4-methylphenol.
  • the plasticizer is DINP.
  • the light-curing two-component polyurea waterproof coating is prepared by the following method:
  • the mass ratio of component A and component B is 1:1. After stirring and mixing, it is coated on the construction base, and then uniformly irradiated with 340nm ultraviolet light to form a film.
  • Table 1 is the raw material formula (in mass kg) of the light-cured two-component polyurea waterproof coatings of Examples 1-3 and Comparative Examples 1-4
  • Table 2 is the performance test results of the polyurea waterproof coatings of Examples 1-3 and Comparative Examples 1-4

Abstract

本发明涉及一种光固化双组份聚脲防水涂料及其制备方法，由A组分和B组分组成，A组分的原料配方包括聚脲预聚体和丙烯酸改性聚脲预聚体，其中，聚脲预聚体是通过异氰酸酯和位阻仲胺进行反应制得；B组分的原料配方包括端氨基聚醚、胺类扩链剂、光引发剂、消泡剂、抗氧剂和增塑剂；其中，位阻仲胺、胺类扩链剂分别选自天门冬氨酸酯类位阻型仲胺。本发明同时在A组分和B组分中均引入天门冬氨酸酯类化合物，配合光引发剂的使用，使得涂料通过紫外线照射后可实现快速深层干燥固化成膜，具有耐候性好，且引入丙烯酸改性，使得涂料同时具有聚氨酯的柔韧性，也有丙烯酸的硬度，并且还具有优异的粘结性，自修复自愈合性能卓越，且开放时间长。

Description

一种光固化双组份聚脲防水涂料及其制备方法 技术领域
本发明属于防水涂料领域，具体涉及一种光固化双组份聚脲防水涂料及其制备方法。
背景技术
聚脲涂料是国内外今年来发展起来的一类反应型、无污染的高性能涂料。近年来发展起来一种聚天门冬氨酸酯聚脲涂料，将聚天门冬氨酸酯引入聚脲涂料中，使得聚天门冬氨酸酯聚脲涂料具有优异的耐候性、流平性好等优点。
如中国专利CN111793420A公开的一种改性聚天门冬氨酸酯聚脲涂料及其制备方法，该聚脲涂料由A组分和B组分构成，其中，按重量份计，A组分物质组成为异氰酸酯和/或异氰酸酯的多聚体；B组分物质组成为20～75份有机硅和环氧双重改性聚天门冬氨酸酯树脂、5～35份填料、0.1～5份颜料、0.5～10份助剂和5～30份溶剂。该聚脲涂料改善了聚脲涂料的低温柔韧性、粘结强度、耐候性及机械性能。然而还存在固化交联需要依赖环境温度，深层固化上强度需要时间，施工效率不高的问题。
发明内容
发明目的：为了解决现有技术存在的问题，本发明提供一种光固化的双组份聚脲防水涂料及其制备方法，通过紫外光照射后可实现快速深层干燥固化成膜，还有优异的粘结性及自修复自愈合性能卓越。
技术方案：为了解决上述技术问题，本发明采用如下技术方案：
一种光固化双组份聚脲防水涂料，由A组分和B组分组成，所述A组分的原料配方包括聚脲预聚体和丙烯酸改性聚脲预聚体，其中，所述聚脲预聚体是通过异氰酸酯和位阻仲胺进行反应制得；
按重量百分含量计，所述B组分的原料配方包括以下组分：
Figure PCTCN2021123453-appb-000001
Figure PCTCN2021123453-appb-000002
其中，所述位阻仲胺、胺类扩链剂分别独立地选自式I所示的天门冬氨酸酯类位阻型仲胺化合物中的一种或几种的组合：
Figure PCTCN2021123453-appb-000003
式I中，X为碳原子数1‐3的烷基，R 1、R 2、R 3、R 4分别独立地选自碳原子数2‐8的直链或支链烷基、—R 5Ph或碳原子数为6‐10的环状烷基，R 5为碳原子数为1‐4的烷基。
根据本发明的一些实施方面，所述式I中，X为CH 2，R 1、R 2、R 3、R 4分别独立地为CH 2CH 3、—R 5Ph或碳原子数为6‐10的环状烷基，R 5为碳原子数为1‐4的烷基。
根据本发明的一些实施方面，所述丙烯酸改性聚脲预聚体是通过含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂与所述聚脲预聚体进行反应制得，其中，所述含羟基的丙烯酸酯为丙烯酸羟乙酯、甲基丙烯酸羟乙酯中的一种或几种，所述含羟基的丙烯酸树脂为羟基丙烯酸树脂。
在一些优选且具体实施方式中，所述羟基丙烯酸树脂为昆山卡斯特高分子材料的羟基丙烯酸树脂HAR863、羟基丙烯酸树脂HAR864、羟基丙烯酸树脂HAR865、羟基丙烯酸树脂HAR867、羟基丙烯酸树脂HAR869、羟基丙烯酸树脂HAR887、羟基丙烯酸树脂HAR960、羟基丙烯酸树脂HAR970中的一种或几种。
根据本发明的一些优选且具体实施方面，所述聚脲预聚体与含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂之间的质量比为0.1‐1：1。
本发明中，通过丙烯酸改性，丙烯酸的引入使得丙烯酸双键在光引发剂的作用下可实现交联固化反应，且丙烯酸接枝到聚脲主链上，实现封端和提供交联点。
根据本发明的一些实施方面，所述异氰酸酯为MDI、TDI、IPDI、HDI、氢化MDI、XDI中的一种或几种。优选地，所述异氰酸酯为MDI。采用MDI更有助于获得优异拉 伸强度和延伸率的材料。
根据本发明的一些实施方面，所述位阻仲胺与异氰酸酯之间的投料质量比为1‐3:1。
根据本发明的一些实施方面，所述A组分中，所述聚脲预聚体和丙烯酸改性聚脲预聚体的质量比例为0.25‐5：1。优选地，所述A组分中，所述聚脲预聚体和丙烯酸改性聚脲预聚体的质量比例为0.8‐1.2：1。
根据本发明的一些实施方面，所述光引发剂为氟化二苯基钛茂、双(五氟苯基)钛茂、二苯酮衍生物、硫杂蒽酮衍生物、烷基芳酮衍生物、苯偶酰衍生物中的一种或几种。在一些优选且具体实施方式中，所述光引发剂为天津久日新材JRCure‐1055、JRCure‐1065、JRCure‐1103、JRCure‐1104、JRCure‐1107、JRCure‐1108、JRCure‐1110、JRCure‐1112、JRCure‐1113、JRCure‐1114、JRCure‐1116中的一种或几种。
根据本发明的一些实施方面，所述端氨基聚醚为伯氨基聚醚、仲氨基聚醚中的一种或几种。在一些优选且具体实施方式中，所述伯氨基聚醚为亨斯曼公司的D230、D400、D2000、D4000、T403、T3000、T5000中的一种或几种，所述仲氨基聚醚为亨斯曼公司的SD231、SD401、SD2001中的一种或几种。
根据本发明的一些实施方面，所述消泡剂为物理消泡剂、化学消泡剂中的一种或几种。在一些优选且具体实施方式中，所述物理消泡剂为聚硅氧烷消泡剂和/或硅酮类消泡剂，所述化学消泡剂为氧化钙、氧化镁、氢氧化钙、恶唑烷类潜固化剂、酮亚胺类潜固化剂的一种或几种的组合。
根据本发明的一些实施方面，所述抗氧剂为2，6‐三级丁基‐4‐甲基苯酚、双(3，5‐三级丁基‐4‐羟基苯基)硫醚、四〔β‐(3，5‐三级丁基‐4‐羟基苯基)丙酸〕季戊四醇酯中的一种或多种的组合。
根据本发明的一些实施方面，所述增塑剂为环烷油、氯化石蜡、DINP、DIDP、DOTP、植物油脂等的其中至少一种。
根据本发明的一些实施方面，所述A组分和B组分的质量比为1:0.8～1.2。本发明的A组分和B组分混合后，A组分中的聚脲预聚体和丙烯酸改性聚脲预聚体可先与B组分中氨基材料反应，形成初始的分子交联架构，然后丙烯酸中的碳碳双键紫外光照射后可实现快速深层干燥固化成膜，迅速交联固化达到最终强度，还有优异的粘结性及自修复自愈合性能卓越。
本发明采取的另一技术方案：上述所述的光固化双组份聚脲防水涂料的制备方法，所述制备方法包括以下步骤：
(1)聚脲预聚体的制备
将位阻仲胺在100～130℃下脱水至水分含量300ppm以下，加入异氰酸酯，在70～100℃下进行反应，制得聚脲预聚体；
(2)丙烯酸改性聚脲预聚体的制备
将步骤(1)制得的聚脲预聚体、含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂、阻聚剂混合，在70～100℃下进行反应，制得丙烯酸改性聚脲预聚体；
(3)A组分的制备
将步骤(1)制得的聚脲预聚体、步骤(2)制得的丙烯酸改性聚脲预聚体混合，制得A组分；
(4)B组分的制备
将端氨基聚醚、胺类扩链剂、增塑剂混合并在100～130℃下脱水至水分含量300ppm以下，降温至50～60℃，加入光引发剂、消泡剂、抗氧剂混合，制得B组分。
进一步地，步骤(1)中，所述位阻仲胺与异氰酸酯的投料质量比为0.2‐3:1。优选地，所述位阻仲胺与异氰酸酯的投料质量比为1～3:1。
根据本发明的一些优选且具体实施方式，步骤(1)的具体实施为：将位阻仲胺在100～130℃下脱水至水分含量300ppm以下，滴加异氰酸酯，70～100℃反应2～4h，取样测试NCO的质量分数达到设计值1‐5％，结束反应，制得聚脲预聚体。
进一步地，步骤(2)中，所述聚脲预聚体、含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂、阻聚剂的投料比例为0.1‐1:1:0.005‐0.015。
根据本发明的一些优选且具体实施方式，步骤(2)的具体实施为：将聚脲预聚体、含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂、阻聚剂混合，70～100℃反应4～6h，测定NCO的质量分数达到设计值，结束反应，制得丙烯酸改性聚脲预聚体。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
本发明的聚脲防水涂料，同时在A组分和B组分中均引入天门冬氨酸酯类化合物，配合光引发剂的使用，使得制备得到的聚脲防水涂料通过紫外线照射后可实现快速深层干燥固化成膜，具有耐候性好，且引入丙烯酸改性，使得聚脲防水涂料同时具有聚氨酯的柔韧性，也有丙烯酸的硬度。
本发明的聚脲防水涂料还具有优异的粘结性，自修复自愈合性能卓越，且开放时间长。
本发明的聚脲防水涂料为100％固含量，安全环保，无刺激气味，施工粘度低，可实现喷涂施工，且可用于低压喷涂机施工，材料凝胶速度快。
具体实施方式
下面结合具体实施例详细说明本发明的技术方案，以便本领域技术人员更好理解和实施本发明的技术方案，但并不因此将本发明限制在所述的实例范围之中。
实施例1
本实施例提供的光固化双组份聚脲防水涂料，其原料配方参见表1所示，其中，
位阻仲胺具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000004
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
异氰酸酯为MDI‐MIPS。
端氨基聚醚为亨斯曼SD2001。
胺类扩链剂具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000005
Figure PCTCN2021123453-appb-000006
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
光引发剂为JRCURE‐1110。
消泡剂为聚硅氧烷消泡剂8110。
抗氧剂为2，6‐三级丁基‐4‐甲基苯酚。
增塑剂为DINP
该光固化双组份聚脲防水涂料通过以下方法制备得到：
(1)聚脲预聚体的制备
将300kg JH334胺类扩链剂在110℃，‐0.09到‐0.1MPa负压下脱水2h，至水分含量300ppm以下，降温到50℃以下，滴加200kg MIPS，30分钟滴加完，滴加期间一直开启降温模式，温度不超过70℃，待温度不再上升，加热到70℃反应3h，取样测试NCO的质量分数达到设计值3％，结束反应，制得500kg聚脲预聚体。
(2)丙烯酸改性聚脲预聚体的制备
将步骤(1)制得的250kg聚脲预聚体、500kg含羟基的丙烯酸酯HAR864、5kg 705阻聚剂混合，在80℃下进行反应，制得755kg丙烯酸改性聚脲预聚体；
(3)A组分的制备
将步骤(1)制得的250kg聚脲预聚体、步骤(2)制得的250kg丙烯酸改性聚脲
预聚体混合，制得A组分500kg；
(4)B组分的制备
将端氨基聚醚D2001 100kg、JH344 150kg、增塑剂DINP 250kg混合并在110℃、‐0.09到‐0.1MPa真空度下脱水至水分含量300ppm以下，降温至50～60℃，加入光引发剂为JRCURE‐1110 0.5kg，消泡剂为聚硅氧烷消泡剂8110 0.5kg，抗氧剂为2，6‐三级丁基‐4‐甲基苯酚1kg，制得502kg B组分。
(5)双组份聚脲防水涂料的制备
A组分和B组分的质量比为1:1，搅拌混合后，涂覆于施工基面上，然后通过340nm的紫外光进行均匀照射固化成膜。
实施例2
本实施例提供的光固化双组份聚脲防水涂料，与实施例1的不同之处在于：A组分中，聚脲预聚体和丙烯酸改性聚脲预聚体的投料质量比不同。
本例中，A、B组分的原料配方参见表1所示，其中，位阻仲胺具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000007
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
异氰酸酯为MDI‐MIPS。
端氨基聚醚为亨斯曼SD2001。
胺类扩链剂具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000008
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
光引发剂为JRCURE‐1110。
消泡剂为聚硅氧烷消泡剂8110。
抗氧剂为2，6‐三级丁基‐4‐甲基苯酚。
增塑剂为DINP。
该光固化双组份聚脲防水涂料通过以下方法制备得到：
(1)聚脲预聚体的制备
将300kg JH334胺类扩链剂在110℃，‐0.09到‐0.1MPa负压下脱水2h，至水分含 量300ppm以下，降温到50℃以下，滴加200kg MIPS，30分钟滴加完，滴加期间一直开启降温模式，温度不超过70℃，待温度不再上升，加热到70℃反应3h，取样测试NCO的质量分数达到设计值3％，结束反应，制得500kg聚脲预聚体。
(2)丙烯酸改性聚脲预聚体的制备
将步骤(1)制得的250kg聚脲预聚体、500kg含羟基的丙烯酸酯HAR864、5kg 705阻聚剂混合，在80℃下进行反应，制得755kg丙烯酸改性聚脲预聚体；
(3)A组分的制备
将步骤(1)制得的100kg聚脲预聚体、步骤(2)制得的400kg丙烯酸改性聚脲预聚体混合，制得A组分500kg；
(4)B组分的制备
将端氨基聚醚D2001 100kg、JH344 150kg、增塑剂DINP 250kg混合并在110℃、‐0.09到‐0.1MPa真空度下脱水至水分含量300ppm以下，降温至50～60℃，加入光引发剂为JRCURE‐1110 0.5kg，消泡剂为聚硅氧烷消泡剂8110 0.5kg，抗氧剂为2，6‐三级丁基‐4‐甲基苯酚1kg，制得502kg B组分。
(5)双组份聚脲防水涂料的制备
A组分和B组分的质量比为1:1，搅拌混合后，涂覆于施工基面上，然后通过340nm的紫外光进行均匀照射固化成膜。
实施例3
本实施例提供的光固化双组份聚脲防水涂料，与实施例1的不同之处在于：A组分中，聚脲预聚体和丙烯酸改性聚脲预聚体的投料质量比不同。
本例中，A、B组分的原料配方参见表1所示，其中，
位阻仲胺具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000009
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
异氰酸酯为MDI‐MIPS。
端氨基聚醚为亨斯曼SD2001。
胺类扩链剂具有以下结构，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000010
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
光引发剂为JRCURE‐1110。
消泡剂为聚硅氧烷消泡剂8110。
抗氧剂为2，6‐三级丁基‐4‐甲基苯酚。
增塑剂为DINP。
该光固化双组份聚脲防水涂料通过以下方法制备得到：
(1)聚脲预聚体的制备
将300kg JH334胺类扩链剂在110℃，‐0.09到‐0.1MPa负压下脱水2h，至水分含量300ppm以下，降温到50℃以下，滴加200kg MIPS，30分钟滴加完，滴加期间一直开启降温模式，温度不超过70℃，待温度不再上升，加热到70℃反应3h，取样测 试NCO的质量分数达到设计值3％，结束反应，制得500kg聚脲预聚体。
(2)丙烯酸改性聚脲预聚体的制备
将步骤(1)制得的250kg聚脲预聚体、500kg含羟基的丙烯酸酯HAR864、5kg 705阻聚剂混合，在80℃下进行反应，制得755kg丙烯酸改性聚脲预聚体；
(3)A组分的制备
将步骤(1)制得的400kg聚脲预聚体、步骤(2)制得的100kg丙烯酸改性聚脲预聚体混合，制得A组分500kg；
(4)B组分的制备
将端氨基聚醚D2001 100kg、JH344 150kg、增塑剂DINP 250kg混合并在110℃、‐0.09到‐0.1MPa真空度下脱水至水分含量300ppm以下，降温至50～60℃，加入光引发剂为JRCURE‐1110 0.5kg，消泡剂为聚硅氧烷消泡剂8110 0.5kg，抗氧剂为2，6‐三级丁基‐4‐甲基苯酚1kg，制得502kg B组分。
(5)双组份聚脲防水涂料的制备：
A组分和B组分的质量比为1:1，搅拌混合后，涂覆于施工基面上，然后通过340nm的紫外光进行均匀照射固化成膜。
对比例1
本实施例提供的光固化双组份聚脲防水涂料，与实施例1的不同之处在于：A组分中不添加聚脲预聚体。
本例中，A组分、B组分的原料配方参见表1所示，其中，
位阻仲胺具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000011
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
异氰酸酯为MDI‐MIPS。
端氨基聚醚为亨斯曼SD2001。
胺类扩链剂具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000012
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
光引发剂为JRCURE‐1110。
消泡剂为聚硅氧烷消泡剂8110。
抗氧剂为2，6‐三级丁基‐4‐甲基苯酚。
增塑剂为DINP。
该光固化双组份聚脲防水涂料通过以下方法制备得到：
(1)聚脲预聚体的制备
将300kg JH334胺类扩链剂在110℃，‐0.09到‐0.1MPa负压下脱水2h，至水分含量300ppm以下，降温到50℃以下，滴加200kg MIPS，30分钟滴加完，滴加期间一直开启降温模式，温度不超过70℃，待温度不再上升，加热到70℃反应3h，取样测试NCO的质量分数达到设计值3％，结束反应，制得500kg聚脲预聚体。
(2)丙烯酸改性聚脲预聚体的制备
将步骤(1)制得的250kg聚脲预聚体、500kg含羟基的丙烯酸酯HAR864、5kg 705阻聚剂混合，在80℃下进行反应，制得755kg丙烯酸改性聚脲预聚体。
(3)A组分的制备
将步骤(1)制得的0kg聚脲预聚体、步骤(2)制得的500kg丙烯酸改性聚脲预
聚体混合，制得A组分500kg。
(4)B组分的制备
将端氨基聚醚D2001 100kg、JH344 150kg、增塑剂DINP 250kg混合并在110℃、‐0.09到‐0.1MPa真空度下脱水至水分含量300ppm以下，降温至50～60℃，加入光引发剂为JRCURE‐1110 0.5kg，消泡剂为聚硅氧烷消泡剂8110 0.5kg，抗氧剂为2，6‐三级丁基‐4‐甲基苯酚1kg，制得502kg B组分。
(5)双组份聚脲防水涂料的制备
A组分和B组分的质量比为1:1，搅拌混合后，涂覆于施工基面上，然后通过340nm的紫外光进行均匀照射固化成膜。
对比例2
本例提供的双组份聚脲防水涂料，与实施例1的不同之处在于：不添加光引发剂。
本例中，A组分、B组分的原料配方参见表1所示，其中，
位阻仲胺具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000013
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
异氰酸酯为MDI‐MIPS。
端氨基聚醚为亨斯曼SD2001。
胺类扩链剂具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000014
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
消泡剂为聚硅氧烷消泡剂8110。
抗氧剂为2，6‐三级丁基‐4‐甲基苯酚。
增塑剂为DINP。
该双组份聚脲防水涂料通过以下方法制备得到：
(1)聚脲树脂的制备
将300kg JH334胺类扩链剂在110℃，‐0.09到‐0.1MPa负压下脱水2h，至水分含量300ppm以下，降温到50℃以下，滴加200kg MIPS，30分钟滴加完，滴加期间一直开启降温模式，温度不超过70℃，待温度不再上升，加热到70℃反应3h，取样测试NCO的质量分数达到设计值3％，结束反应，制得500kg聚脲预聚体。
(2)丙烯酸改性聚脲预聚体的制备
将步骤(1)制得的250kg聚脲预聚体、500kg含羟基的丙烯酸酯HAR864、5kg 705阻聚剂混合，在80℃下进行反应，制得755kg丙烯酸改性聚脲预聚体。
(3)A组分的制备
将步骤(1)制得的250kg聚脲预聚体、步骤(2)制得的250kg丙烯酸改性聚脲
预聚体混合，制得A组分500kg
(4)B组分的制备
将端氨基聚醚D2001 100kg、JH344 150kg、增塑剂DINP 250kg混合并在110℃、‐0.09到‐0.1MPa真空度下脱水至水分含量300ppm以下，降温至50～60℃，消泡剂为聚硅氧烷消泡剂8110 0.5kg，抗氧剂为2，6‐三级丁基‐4‐甲基苯酚1kg，制得501.5kg B组分。
(5)双组份聚脲防水涂料的制备
A组分和B组分的质量比为1:1，搅拌混合后，涂覆于施工基面上，然后通过340nm的紫外光进行均匀照射固化成膜。
对比例3
本例提供的双组份聚脲防水涂料，与实施例1的不同之处在于：胺类扩链剂采用unilink4200。
本例中，A组分、B组分的原料配方参见表1所示其中，
位阻仲胺为unilink4200。
异氰酸酯为MDI‐MIPS。
端氨基聚醚为亨斯曼SD2001。
胺类扩链剂为unilink4200。
光引发剂为JRCURE‐1110。
消泡剂为聚硅氧烷消泡剂8110。
抗氧剂为2，6‐三级丁基‐4‐甲基苯酚。
增塑剂为DINP。
该光固化双组份聚脲防水涂料通过以下方法制备得到：
(1)聚脲树脂的制备
将300kg unilink4200胺类扩链剂在110℃，‐0.09到‐0.1MPa负压下脱水2h，至水分含量300ppm以下，降温到50℃以下，滴加200kg MIPS，30分钟滴加完，滴加期间一直开启降温模式，温度不超过70℃，待温度不再上升，加热到70℃反应3h，取样测试NCO的质量分数达到设计值3％，结束反应，制得500kg聚脲预聚体。
(2)丙烯酸改性聚脲预聚体的制备
将步骤(1)制得的250kg聚脲预聚体、500kg含羟基的丙烯酸酯HAR864、5kg 705阻聚剂混合，在80℃下进行反应，制得755kg丙烯酸改性聚脲预聚体。
(3)A组分的制备
将步骤(1)制得的250kg聚脲预聚体、步骤(2)制得的250kg丙烯酸改性聚脲
预聚体混合，制得A组分500kg。
(4)B组分的制备
将端氨基聚醚D2001 100kg、unilink4200 150kg、增塑剂DINP 250kg混合并在110℃、‐0.09到‐0.1MPa真空度下脱水至水分含量300ppm以下，降温至50～60℃，加 入光引发剂为JRCURE‐1110 0.5kg，消泡剂为聚硅氧烷消泡剂8110 0.5kg，抗氧剂为2，6‐三级丁基‐4‐甲基苯酚1kg，制得502kg B组分。
(5)双组份聚脲防水涂料的制备
A组分和B组分的质量比为1:1，搅拌混合后，涂覆于施工基面上，然后通过340nm的紫外光进行均匀照射固化成膜。
对比例4
本例提供的双组份聚脲防水涂料，与实施例1的不同之处在于：A组分采用异氰酸酯为TDI。
本例中，A组分、B组分的原料配方参见表1所示，其中，
位阻仲胺具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000015
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
异氰酸酯为TDI。
端氨基聚醚为亨斯曼SD2001。
胺类扩链剂具有以下结构式，具体选用骏和化工(上海)有限公司的JH334，简称胺类扩链剂1号：
Figure PCTCN2021123453-appb-000016
式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
光引发剂为JRCURE‐1110。
消泡剂为聚硅氧烷消泡剂8110。
抗氧剂为2，6‐三级丁基‐4‐甲基苯酚。
增塑剂为DINP。
该光固化双组份聚脲防水涂料通过以下方法制备得到：
(1)聚脲预聚体的制备
将300kg JH334胺类扩链剂在110℃，‐0.09到‐0.1MPa负压下脱水2h，至水分含量300ppm以下，降温到50℃以下，滴加200kg tdi，30分钟滴加完，滴加期间一直开启降温模式，温度不超过70℃，待温度不再上升，加热到70℃反应3h，取样测试NCO的质量分数达到设计值3％，结束反应，制得500kg聚脲预聚体。
(2)丙烯酸改性聚脲预聚体的制备
将步骤(1)制得的250kg聚脲预聚体、500kg含羟基的丙烯酸酯HAR864、5kg 705阻聚剂混合，在80℃下进行反应，制得755kg丙烯酸改性聚脲预聚体。
(3)A组分的制备
将步骤(1)制得的250kg聚脲预聚体、步骤(2)制得的250kg丙烯酸改性聚脲预聚体混合，制得A组分500kg。
(4)B组分的制备
将端氨基聚醚D2001 100kg、JH344 150kg、增塑剂DINP 250kg混合并在110℃、‐0.09到‐0.1MPa真空度下脱水至水分含量300ppm以下，降温至50～60℃，消泡剂为聚硅氧烷消泡剂8110 0.5kg，抗氧剂为2，6‐三级丁基‐4‐甲基苯酚1kg，制得502kg B组分。
(5)双组份聚脲防水涂料的制备
A组分和B组分的质量比为1:1，搅拌混合后，涂覆于施工基面上，然后通过340nm的紫外光进行均匀照射固化成膜。
表1为实施例1～3和对比例1～4的光固化双组份聚脲防水涂料的原料配方(以质量kg计)
Figure PCTCN2021123453-appb-000017
Figure PCTCN2021123453-appb-000018
将实施例1～3和对比例1～4的聚脲防水涂料参照GB/T19250‐2013聚氨酯防水涂料标准进行性能检测，结果如表2所示。
表2为实施例1～3和对比例1～4的聚脲防水涂料的性能测试结果
Figure PCTCN2021123453-appb-000019
Figure PCTCN2021123453-appb-000020
由表2的测试数据可知，聚脲预聚体和丙烯酸改性聚脲预聚体比例需要达到1比1左右方能发挥最好效果，不加引发剂，材料固化不充分对性能有极大影响，换其他胺类扩链剂材料弹性恢复率差，说明自聚合能力不足，换TDI后材料强度降低延伸率等都有所降低。
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。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。

Claims (15)

  1. 一种光固化双组份聚脲防水涂料，由A组分和B组分组成，其特征在于，
    所述A组分的原料配方包括聚脲预聚体和丙烯酸改性聚脲预聚体，其中，所述聚脲预聚体是通过异氰酸酯和位阻仲胺进行反应制得；
    所述丙烯酸改性聚脲预聚体是通过含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂与所述聚脲预聚体进行反应制得，其中，所述含羟基的丙烯酸酯为丙烯酸羟乙酯、甲基丙烯酸羟乙酯中的一种或几种，所述含羟基的丙烯酸树脂为羟基丙烯酸树脂；所述聚脲预聚体与含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂之间的质量比为0.1‐1:1；
    所述A组分中，所述聚脲预聚体和丙烯酸改性聚脲预聚体的质量比为0.8‐1.2：1。
    按重量百分含量计，所述B组分的原料配方包括以下组分：
    Figure PCTCN2021123453-appb-100001
    其中，所述位阻仲胺、胺类扩链剂分别独立地选自式I所示的天门冬氨酸酯类位阻型仲胺化合物中的一种或几种：
    Figure PCTCN2021123453-appb-100002
    式I中，X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3；
    所述异氰酸酯为MDI；
    所述A组分和B组分的质量比为1:0.8～1.2。
  2. 根据权利要求1所述的光固化双组份聚脲防水涂料，其特征在于：所述聚脲 预聚体和丙烯酸改性聚脲预聚体的质量比例为1：1。
  3. 一种光固化双组份聚脲防水涂料，由A组分和B组分组成，其特征在于，
    所述A组分的原料配方包括聚脲预聚体和丙烯酸改性聚脲预聚体，其中，所述聚脲预聚体是通过异氰酸酯和位阻仲胺进行反应制得；
    按重量百分含量计，所述B组分的原料配方包括以下组分：
    Figure PCTCN2021123453-appb-100003
    其中，所述位阻仲胺、胺类扩链剂分别独立地选自式I所示的天门冬氨酸酯类位阻型仲胺化合物中的一种或几种：
    Figure PCTCN2021123453-appb-100004
    式I中，X为碳原子数1‐3的烷基，R 1、R 2、R 3、R 4分别独立地选自碳原子数2‐8的直链或支链烷基、—R 5Ph或碳原子数为6‐10的环状烷基，R 5为碳原子数为1‐4的烷基。
  4. 根据权利要求3所述的光固化双组份聚脲防水涂料，其特征在于：所述丙烯酸改性聚脲预聚体是通过含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂与所述聚脲预聚体进行反应制得，其中，所述含羟基的丙烯酸酯为丙烯酸羟乙酯、甲基丙烯酸羟乙酯中的一种或几种，所述含羟基的丙烯酸树脂为羟基丙烯酸树脂。
  5. 根据权利要求4所述的光固化双组份聚脲防水涂料，其特征在于：所述聚脲预聚体与含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂之间的质量比为0.1‐1:1。
  6. 根据权利要求3所述的光固化双组份聚脲防水涂料，其特征在于：所述异氰酸酯为MDI、TDI、IPDI、HDI、氢化MDI、XDI中的一种或几种。
  7. 根据权利要求6所述的光固化双组份聚脲防水涂料，其特征在于：所述异氰酸酯为MDI。
  8. 根据权利要求3所述的光固化双组份聚脲防水涂料，其特征在于：所述位阻仲胺与异氰酸酯的投料质量比为0.2‐3:1。
  9. 根据权利要求8所述的光固化双组份聚脲防水涂料，其特征在于：所述位阻仲胺与异氰酸酯之间的投料质量比为1‐3:1。
  10. 根据权利要求3所述的光固化双组份聚脲防水涂料，其特征在于：所述A组分中，所述聚脲预聚体和丙烯酸改性聚脲预聚体的质量比例为0.25‐5：1。
  11. 根据权利要求10所述的光固化双组份聚脲防水涂料，其特征在于：所述聚脲预聚体和丙烯酸改性聚脲预聚体的质量比例为1～4:1。
  12. 根据权利要求3所述的光固化双组份聚脲防水涂料，其特征在于：所述X为CH 2，R 1、R 2、R 3、R 4分别为CH 2CH 3。
  13. 根据权利要求3所述的光固化双组份聚脲防水涂料，其特征在于：所述光引发剂为氟化二苯基钛茂、双(五氟苯基)钛茂、二苯酮衍生物、硫杂蒽酮衍生物、烷基芳酮衍生物、苯偶酰衍生物中的一种或几种；所述端氨基聚醚为伯氨基聚醚、仲氨基聚醚中的一种或几种。
  14. 根据权利要求3所述的光固化双组份聚脲防水涂料，其特征在于：所述A组分和B组分的质量比为1:0.8～1.2。
  15. 权利要求3～14中任一项权利要求所述的光固化双组份聚脲防水涂料的制备方法，其特征在于，所述制备方法包括以下步骤：
    (1)聚脲预聚体的制备
    将位阻仲胺在100～130℃下脱水至水分含量300ppm以下，加入异氰酸酯，在70～100℃下进行反应，制得聚脲预聚体；
    (2)丙烯酸改性聚脲预聚体的制备
    将步骤(1)制得的聚脲预聚体、含羟基的丙烯酸酯和/或含羟基的丙烯酸树脂、阻聚剂混合，在70～100℃下进行反应，制得丙烯酸改性聚脲预聚体；
    (3)A组分的制备
    将步骤(1)制得的聚脲预聚体、步骤(2)制得的丙烯酸改性聚脲预聚体混合，制得A组分；
    (4)B组分的制备
    将端氨基聚醚、胺类扩链剂、增塑剂混合并在100～130℃下脱水至水分含量300ppm以下，降温至50～60℃，加入光引发剂、消泡剂、抗氧剂混合，制得B组分。
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