WO2021088416A1 - 脂肪族多异氰酸酯组合物、其制备方法及涂料组合物 - Google Patents

脂肪族多异氰酸酯组合物、其制备方法及涂料组合物 Download PDF

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Publication number
WO2021088416A1
WO2021088416A1 PCT/CN2020/103277 CN2020103277W WO2021088416A1 WO 2021088416 A1 WO2021088416 A1 WO 2021088416A1 CN 2020103277 W CN2020103277 W CN 2020103277W WO 2021088416 A1 WO2021088416 A1 WO 2021088416A1
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diisocyanate
composition
reaction
aliphatic
aliphatic polyisocyanate
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PCT/CN2020/103277
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English (en)
French (fr)
Inventor
邱化敏
付帅
王家发
周建强
王庆义
周芸
黄长荣
李晶
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万华化学集团股份有限公司
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Application filed by 万华化学集团股份有限公司 filed Critical 万华化学集团股份有限公司
Priority to EP20885750.8A priority Critical patent/EP4056618A4/en
Priority to US17/636,736 priority patent/US20220298293A1/en
Priority to KR1020227019306A priority patent/KR20220101649A/ko
Publication of WO2021088416A1 publication Critical patent/WO2021088416A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing isocyanurate 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1883—Catalysts containing secondary or tertiary amines or salts thereof having heteroatoms other than oxygen and nitrogen
    • 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
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
    • 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
    • C08G18/40—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
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • 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
    • 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

Definitions

  • the invention relates to the field of coatings, in particular to an aliphatic polyisocyanate composition, a preparation method thereof, and a coating composition obtained from the aliphatic polyisocyanate composition.
  • the viscosity of the aliphatic polyisocyanate is very dependent on the type of the raw material diisocyanate, the conversion rate of the reaction and the composition of the product. Generally, the higher the conversion rate of the reaction is, the higher the product viscosity is under the condition of a certain type of the raw material aliphatic diisocyanate. At a comparable conversion rate, the higher the proportion of the polymer containing iminooxadiazinedione structure, the lower the viscosity of the aliphatic polyisocyanate.
  • the iminooxadiazinedione structure polymer in the product must be maintained at an appropriate ratio. Achieve low viscosity while ensuring excellent film performance.
  • CN 106604944A discloses a polyisocyanate composition, a coating composition, a coating film and a method for making the same, and a method for stabilizing moisture, wherein the ratio of iminooxadiazinedione structure/isocyanurate structure polymer is limited In the range of 0.0005 to 0.3, it shows that by setting the above molar ratio to 0.30 or less, a coating film with excellent adhesion to the base coating film can be formed, which means that the content of the iminooxadiazinedione structure polymer is actually There is an impact on the performance of the paint film, but it does not further disclose the reasons for the above impact.
  • WO 2007046470A1 discloses a highly crosslinkable, low-viscosity polyisocyanate composition and a coating composition containing the same, which controls the isocyanurate in the composition, allophanate prepared from alcohol, and uretdione
  • the uretdione structure actually forms a linear polymer during crosslinking, which has an adverse effect on the hardness and weather resistance of the paint film.
  • CN 101165048A discloses a preparation method of polyisocyanate containing iminooxadiazinedione structure polymer, wherein it is disclosed that the iminooxadiazinedione structure has reduced polyisocyanate viscosity, and has a higher viscosity than crosslinked product
  • the linear uretdione structure has better crosslinking properties (see Proc. of XXIVth Fatipec Conference, 8-11 June 1998, Interlaken, CH, Vol. D, pp. D-136-137).
  • an object of the present invention is to provide an aliphatic polyisocyanate composition, which has a lower viscosity while ensuring the performance of the resulting paint film.
  • Another object of the present invention is to provide a method for preparing an aliphatic polyisocyanate composition.
  • Another object of the present invention is to provide a coating composition.
  • the aliphatic polyisocyanate composition provided by the present invention is prepared with an aliphatic diisocyanate as a starting material, and is composed of a three-molecular polymer formed by the aliphatic diisocyanate and a polymer having more than three molecules, in the composition It has an iminooxadiazinedione structure (as shown in formula 1) and an isocyanurate structure (as shown in formula 2), wherein the iminooxadiazinedione structure in the composition is the same as
  • the molar ratio of the isocyanurate structure in the composition is 0.01 to 0.8:1, and the iminooxadiazinedione structure in the polymer with more than three molecules and the imino in the composition
  • the molar ratio of the oxadiazinedione structure is 0.2-0.8:1.
  • the aliphatic polyisocyanate composition mainly includes a three-molecular polymer formed by the polymerization of aliphatic diisocyanate in the presence of a catalyst and a polymer larger than three-molecular (other components are negligible).
  • polymers with more than three molecules include five-molecule polymers, seven-molecule polymers, nine-molecular polymers, and multi-molecule polymers.
  • the tri-molecular polymer contains an isocyanurate ring or an iminooxadiazinedione ring, and the N of the ring structure is connected with a diisocyanate monomer to remove residues other than the ring structure.
  • R represents the part of the diisocyanate monomer that does not contain the NCO group.
  • the composition of the five-molecule polymer includes: 1 isocyanurate ring and 1 isocyanurate ring, 1 isocyanurate ring and 1 iminooxadiazinedione ring, and 1
  • the imino oxadiazine dione ring has 1 imino oxadiazine dione ring.
  • the seven-molecule polymer continues to incorporate one isocyanurate ring or one iminooxadiazinedione ring on the basis of the five-molecule polymer. And so on.
  • the iminooxadiazinedione structure in the polyisocyanate composition can reduce the viscosity of the composition, but its thermal stability relative to the isocyanurate structure is poor, so when the content of the iminooxadiazinedione structure is When it is higher, the heat resistance and other properties of the paint film prepared by cross-linking are poor.
  • the present inventors discovered that when a single iminooxadiazinedione ring is further polymerized to form a macromolecular polymer containing a single iminooxadiazinedione ring and one or more isocyanurates, that is When a polymer with an iminooxadiazinedione structure containing more than three molecules is formed, the heat resistance of the paint film prepared after crosslinking can be significantly improved.
  • the molar ratio of the iminooxadiazinedione structure in the composition to the isocyanurate structure in the composition may be 0.01:1, 0.05:1, and 0.08 :1, 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, etc. Any ratio or any combination of ratio intervals.
  • the molar ratio of the iminooxadiazinedione structure in the polymer greater than three molecules to the iminooxadiazinedione structure in the composition may be 0.2:1 , 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, etc. Any ratio or any combination of ratio intervals.
  • the tri-molecular polymer may account for 30-75% of the mass content of the aliphatic polyisocyanate composition, for example, it may be 30%, 35%, 40%, 45%, 50%, Any content value such as 55%, 60%, 65%, 70%, 75% or any combination of content value ranges.
  • the aliphatic diisocyanate can be any known species used to prepare aliphatic polyisocyanates, including but not limited to tetramethylene-1,4-diisocyanate, pentamethylene- 1,5-diisocyanate, hexamethylene-1,6-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, etc.
  • the aliphatic diisocyanate may be hexamethylene-1,6-diisocyanate or isophorone diisocyanate.
  • the preparation method of the aliphatic polyisocyanate composition provided by the present invention includes the following steps:
  • reaction solution I Using an aliphatic diisocyanate as a starting material, the reaction is carried out in the presence of a catalyst A to obtain a reaction solution I, wherein the catalyst A is selected from the group consisting of tetraethylammonium fluoride, tetra-n-butylammonium fluoride, sixteen Alkyl trimethylammonium fluoride, tetramethylammonium triazole salt, tetrabutylphosphine triazole salt or tetrabutylphosphine benzotriazole salt;
  • step S2 Using the reaction liquid I obtained in step S1 as a raw material, continue the reaction in the presence of a catalyst B to obtain a reaction liquid II, wherein the catalyst B is selected from the group consisting of tetramethylammonium acetate, dodecyltrimethyloctanoic acid amine, DABCO TMR or N,N,N-trimethyl-N-hydroxypropyl carboxylic acid quaternary ammonium salt; and
  • the preparation method provided by the present invention in the presence of catalyst A, the resulting reaction solution I contains more iminooxadiazinedione structure, while in the presence of catalyst B, almost no iminooxadiazine is produced Diketone structure, but make the aliphatic diisocyanate further form a polymer, thereby controlling the content and distribution of the iminooxadiazinedione structure in the resultant product, thereby obtaining an aliphatic polyisocyanate composition with excellent performance . Moreover, the preparation method provided by the present invention hardly produces other structures or impurities that affect the properties of the aliphatic polyisocyanate composition.
  • the content and distribution of the iminooxadiazinedione structure may depend on the reaction conversion ratio distribution of step S1 and step S2.
  • step S1 when the reaction conversion rate reaches 1-20%, the reaction is terminated to obtain the reaction liquid I.
  • step S2 when the reaction conversion rate reaches 25-65%, the reaction is terminated to obtain the reaction liquid II.
  • the catalyst A used in the step S1 can also be other catalysts that are compatible with tetraethylammonium fluoride, tetra-n-butylammonium fluoride, cetyltrimethylammonium fluoride, etc.
  • Quaternary ammonium fluoride salts with similar catalytic properties it can also be other quaternary ammonium triazole salts with similar catalytic properties as tetramethylammonium triazole salt, tetrabutylphosphine triazole salt, tetrabutylphosphine benzotriazole salt, etc.
  • Azole salt tetraethylammonium fluoride, tetra-n-butylammonium fluoride, cetyltrimethylammonium fluoride, etc.
  • Quaternary ammonium fluoride salts with similar catalytic properties it can also be other quaternary ammonium triazole salts with similar catalytic properties as
  • the catalyst B used in step S2 can also be other catalysts that are combined with tetramethylammonium acetate, dodecyltrimethyloctanoic acid amine, DABCOTMR, N,N,N-trimethyl -N-hydroxypropyl carboxylic acid quaternary ammonium salt and other carboxylic acid quaternary ammonium salts with similar catalytic properties.
  • reaction temperature in step S1 and step S2 may be 55-70°C.
  • the film evaporation temperature can be 120-180°C.
  • the terminator used to terminate the reaction can be selected according to the types of catalysts A and B, for example, it can be di-n-butyl phosphate.
  • the coating composition provided by the present invention comprises the aliphatic polyisocyanate composition described in any one of the above technical solutions.
  • the coating composition provided by the present invention may also contain any known auxiliary components, including but not limited to acrylic polyols, polyester polyols and the like.
  • the acrylic polyol is selected from polyols polymerized from one or more of the following monomers: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl acrylate. -Hydroxybutyl ester, glycerol monoacrylate or methacrylate monoester, trimethylolpropane monoacrylate or methacrylate monoester;
  • the polyester polyol is selected from succinic acid, adipic acid, One or more carboxylic acids or anhydrides selected from sebacic acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid and selected from ethylene glycol, propylene glycol, diethylene glycol, neopentyl Polyester polyol obtained by condensation reaction of one or more polyols among diol, trimethylolpropane and glycerin.
  • the aliphatic polyisocyanate composition provided by the present invention can also be used in combination with polyisocyanate compositions of other sources or properties in order to adjust the properties of the resulting coating composition.
  • the coating composition provided by the present invention can be prepared through existing technology and existing equipment.
  • the aliphatic polyisocyanate composition provided by the present invention by specifically controlling the content and distribution of the iminooxadiazinedione structure, can have both lower viscosity and better crosslinking properties, and is used in coating compositions. After that, it can significantly reduce the amount of solvent used, is more environmentally friendly, and has better paint film properties, and has been significantly improved in many aspects such as drying speed, paint film hardness, and solvent resistance.
  • the preparation method of the invention has simple process, mild conditions, easy operation and control, and is suitable for industrial-scale production.
  • the mass percentage of each component in the polyisocyanate composition is obtained by gel chromatography, and the mass percentage of the tri-molecular polymer is represented by "TW", and TW is gel chromatography.
  • the medium residence time is 25.25min-26.5min peak area percentage, and the mobile phase of the tri-molecular polymer is collected at the same time.
  • the gel chromatography test method is LC-20AD/RID-10A
  • the column is MZ-Gel SDplus 10E3A 5 ⁇ m (8.0 ⁇ 300mm), MZ-Gel SDplus 500A 5 ⁇ m (8.0 ⁇ 300mm), MZ-Gel SDplus 100A 5 ⁇ m (8.0 ⁇ 300mm) in series, Shimadzu; mobile phase: tetrahydrofuran; flow rate: 1.0 mL/min; analysis time: 40 min, column temperature: 35°C.
  • the sum of the molar proportions of the components in the composition is calculated and added according to the mass proportions of the components obtained by gel chromatography.
  • T isocyanurate structure/(iminooxadiazinedione structure+isocyanurate structure)
  • AT three molecules of iminooxadiazinedione structure/(three molecules of iminooxadiazinedione structure + three Molecular isocyanurate structure
  • test methods of A, T and AT adopt 13 C-NMR nuclear magnetic resonance method.
  • the test of A and T is the collection of the NMR spectrum of the composition (denoted as "spectrum 1")
  • the test of AT is the collection of the NMR spectrum of the tri-molecular polymer components collected by gel chromatography (denoted as " Spectrum 2"), that is, the collected tri-molecular polymer mobile phase is concentrated to remove THF.
  • Isocyanurate structure an absorption peak near 148.4ppm
  • the calculation method of A is: in spectrum 1, the integral value near 135.2ppm/(the integral value near 148.4ppm/3+the integral value near 135.2ppm)
  • T is calculated as follows: In spectrum 1, (integrated value near 148.4ppm/3)/(integrated value near 148.4ppm/3+integrated value near 135.2ppm)
  • the calculation method of AT is: in spectrum 2, the integral value near 135.2ppm/(the integral value near 148.4ppm/3+the integral value near 135.2ppm)
  • the molar ratio of the iminooxadiazinedione structure in the polymer greater than three molecules to the total iminooxadiazinedione structure in the composition is represented by "Y".
  • reaction conversion rate refers to the mass ratio of the aliphatic diisocyanate that has been reacted and converted based on the mass of the starting aliphatic diisocyanate raw material.
  • the other reagents used are all commercially available products unless otherwise specified, and the devices or operating methods used are common devices or operating methods in the art unless otherwise specified.
  • the paint film performance test is carried out according to the following method:
  • Drying time test Use a linear drying time recorder to read the drying time according to the national standard GB/T 1728.
  • Pendulum hardness test Put the sprayed/scratch-coated sample at room temperature for 15-20 minutes, bake at 80°C for 30 minutes, and place it at room temperature for 30 minutes, then test the pendulum hardness test.
  • Ethanol-resistant wipe test After the paint film is scratched, it is baked at 70°C for 30 minutes and placed for 24 hours, and then the solvent-resistant wiper is used for the ethanol wipe test.
  • Reaction a Put 5kg of aliphatic diisocyanate monomer in a four-necked flask, under the protection of nitrogen, heat up to 50°C, add 10ml of tetra-n-butylammonium fluoride (1M THF solution, purchased from Aladdin Reagent Company) under stirring conditions ) Catalyst and start timing. During the reaction, the reaction temperature was controlled at 55°C to 70°C, the aliphatic diisocyanate monomer was quantified by gel chromatography, and the conversion rate of the reaction was monitored. When the specified conversion rate is reached, 0.01 mol of di-n-butyl phosphate terminator is added to terminate the reaction a, and a reaction solution I is obtained.
  • 1M THF solution purchased from Aladdin Reagent Company
  • Reaction b Cool the reaction liquid I to 50°C, add 3ml DABCO TMR (purchased from Evonik) catalyst under stirring conditions, and start timing. During the reaction, the reaction temperature was controlled at 55°C to 70°C, the aliphatic diisocyanate monomer was quantified by gel chromatography, and the conversion rate of the reaction was monitored. When the predetermined conversion rate is reached, 0.01 mol of di-n-butyl phosphate terminator is added to terminate the reaction b, and a reaction solution II is obtained.
  • DABCO TMR purchased from Evonik
  • reaction liquid II was evaporated using a thin film and separated at a temperature of 120-180°C to obtain a light-colored polyisocyanate product, the composition and viscosity of which are shown in Table 1.
  • the viscosity of IPDI polyisocyanate is measured based on a 70% butyl acetate solution.
  • the aliphatic polyisocyanate compositions prepared in Examples 1-4 and Comparative Examples 1-6 were used to prepare coating compositions and perform coating film evaluation.
  • HDI type isocyanate coating composition coating film evaluation formula the HDI type aliphatic polyisocyanate composition prepared by using hydroxypropyl resin (AC1100B) in combination with the above examples and comparative examples, the molar ratio of isocyanate groups to hydroxyl groups is 1.1:1, The solid content of the coating is 40%, the solvent is butyl acetate and xylene, and the mass ratio is 1:1.
  • the evaluation results are shown in Table 2.
  • IPDI-type isocyanate coating composition coating film evaluation formula IPDI-type aliphatic polyisocyanate composition prepared by using hydroxypropyl resin (AC1100B) in combination with the above examples and comparative examples and the commercially available HDI trimer product WANNATE HT-100, IPDI type
  • the mass ratio of aliphatic polyisocyanate composition to WANNATE HT-100 is 1:5, the molar ratio of total isocyanate groups to hydroxyl groups is 1.1:1, the solid content of the coating is 40%, the solvent is butyl acetate and xylene, and the mass ratio is It is 1:1.
  • the evaluation results are shown in Table 3.
  • the aliphatic polyisocyanate composition provided by the present invention can have a lower viscosity by controlling the content and distribution of the iminooxadiazinedione structure, which can be used after coating composition.
  • the prepared paint film has a faster drying speed, better paint film hardness and solvent resistance wiping performance, and the overall performance has been significantly improved, so it has a very promising application prospect.

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Abstract

一种脂肪族多异氰酸酯组合物，其中，亚氨代噁二嗪二酮结构与异氰脲酸酯结构的摩尔比为0.01～0.8：1，且大于三分子聚合物中的亚氨代噁二嗪二酮结构与组合物中的亚氨代噁二嗪二酮结构的摩尔比为0.2～0.8：1。提供了所述脂肪族多异氰酸酯组合物的制备方法以及一种涂料组合物。所述脂肪族多异氰酸酯组合物同时兼具较低的粘度和较好的交联性，在用于涂料组合物后，能够显著减少溶剂的使用量，更加环境友好，而且还具有更好的漆膜性能，制备方法工艺简便，条件温和，易于操作和控制，适宜工业规模的生产。

Description

[根据细则37.2由ISA制定的发明名称]　脂肪族多异氰酸酯组合物、其制备方法及涂料组合物 技术领域
本发明涉及涂料领域，具体涉及一种脂肪族多异氰酸酯组合物、其制备方法以及由所述脂肪族多异氰酸酯组合物所得的涂料组合物。
背景技术
由于具有脂肪族异氰脲酸酯结构的脂肪族多异氰酸酯的优异耐候性，其被广泛用于汽车原厂漆及修补漆等高端领域，特别是清漆。近些年，由于环境保护要求的提高，降低脂肪族多异氰酸酯粘度、减少溶剂用量已成为发展趋势。通常，为实现脂肪族多异氰酸酯的低粘度化并且保持较好的交联性，一般是通过改变催化剂或工艺实现二异氰酸酯三聚生成含异氰脲酸酯结构聚合物的同时，生成一定比例的含亚氨代噁二嗪二酮结构聚合物。
脂肪族多异氰酸酯的粘度十分依赖于原料二异氰酸酯的种类、反应的转化率及产品的组成，一般在原料脂肪族二异氰酸酯种类一定的条件下，反应的转化率越高，产品粘度越高。在相当的转化率下，含亚氨代噁二嗪二酮结构聚合物比例越高，脂肪族多异氰酸酯粘度越低。但由于亚氨代噁二嗪二酮结构稳定性、交联性都明显差于异氰脲酸酯结构，因此，产品中亚氨代噁二嗪二酮结构聚合物必须保持在适当的比例才能实现在粘度低的同时保证优异的漆膜性能。
CN 106604944A公开了一种多异氰酸酯组合物、涂料组合物、涂膜及其制造方法、以及潮湿稳定化方法，其中将亚氨代噁二嗪二酮结构/异氰脲酸酯结构聚合物比例限定在0.0005-0.3，并且说明通过使上述摩尔比率为0.30以下，能形成与基底涂膜的密合性优异的涂膜，也即在说明亚氨代噁二嗪二酮结构聚合物的含量实际上对漆膜的性能是存在影响的，然而其并未进一步披露产生上述影响的原因。
WO 2007046470A1公开了高交联性、低粘度聚异氰酸酯组合物及含其的涂料组合物，其通过控制组合物中的异氰脲酸酯、由醇制备的脲基甲酸酯、脲二酮的比例，实现了产品粘度的降低，然而脲二酮结构在交联时实际形成的是线型的高分子，这对于漆膜的硬度、耐候性是有不利影响的。
CN 101165048A公开了一种含有亚氨代噁二嗪二酮结构聚合物的聚异氰酸酯的制备方法，其中披露了亚氨代噁二嗪二酮结构具有降低多异氰酸酯粘度，并且其具有比交联产物为线性的脲二酮结构更好的交联性(参见Proc.of XXIVth Fatipec Conference,8-11 June 1998,Interlaken,CH,Vol.D,pp.D-136-137)。
通过现有技术可知，在脂肪族多异氰酸酯组合物中引入亚氨代噁二嗪二酮结构能够降低脂肪族多异氰酸酯的粘度，然而，实现引入亚氨代噁二嗪二酮结构的同时保证制备漆膜的优异性能是困难的，因此需要开发一种脂肪族多异氰酸酯，使其降低粘度的同时保持良好的交联性，从而保证所得漆膜的优异性能。
发明内容
为克服现有技术中存在的上述缺陷，本发明的一个目的是提供一种脂肪族多异氰酸酯组合物，其具有较低的粘度的同时还能保证所得漆膜的性能。
本发明的另一目的是提供一种脂肪族多异氰酸酯组合物的制备方法。
本发明的还一目的是提供一种涂料组合物。
本发明提供的脂肪族多异氰酸酯组合物，其以脂肪族二异氰酸酯为起始原料制得，由所述脂肪族二异氰酸酯形成的三分子聚合物和大于三分子聚合物组成，所述组合物中具有亚氨代噁二嗪二酮结构(如式1所示)以及异氰脲酸酯结构(如式2所示)，其中，所述组合物中的亚氨代噁二嗪二酮结构与所述组合物中的异氰脲酸酯结构的摩尔比为0.01～0.8：1，且所述大于三分子聚合物中的亚氨代噁二嗪二酮结构与所述组合物中的亚氨代噁二嗪二酮结构的摩尔比为0.2～0.8：1。
Figure PCTCN2020103277-appb-000001
Figure PCTCN2020103277-appb-000002
通常，脂肪族多异氰酸酯组合物主要包括脂肪族二异氰酸酯在催化剂存在下聚合生成的三分子聚合物及大于三分子聚合物(其他成分可忽略不计)。其中，大于三分子聚合物包括五分子聚合物、七分子聚合物、九分子聚合物、多分子聚合物等。
其中，三分子聚合物中含一个异氰脲酸酯环或含一个含亚氨代噁二嗪二酮环，环结构的N上连接有二异氰酸酯单体除去参与成环结构之外的残基，(分别如式3、4所示)，R表示二异氰酸酯单体不包含NCO基团的部分。
Figure PCTCN2020103277-appb-000003
五分子聚合物的组成包括：1个异氰脲酸酯环并1个异氰脲酸酯环、1个异氰脲酸酯环并1个亚氨代噁二嗪二酮环，和1个亚氨代噁二嗪二酮环并1个亚氨代噁二嗪二酮环。七分子聚合物为在五分子聚合物的基础上继续并入1个异氰脲酸酯环或1个亚氨代噁二嗪二酮环。依次类推。
多异氰酸酯组合物中的亚氨代噁二嗪二酮结构能够降低组合物的粘度，但其相对异氰脲酸酯结构的热稳定性较差，故当亚氨代噁二嗪二酮结构含量较高时，交联制备的漆膜的 耐热性等性能较差。然而，本发明人发现，当单个亚氨代噁二嗪二酮环进一步聚合形成含有单个亚氨代噁二嗪二酮环及一个或多个异氰脲酸酯的大分子聚合物时，即形成含亚氨代噁二嗪二酮结构的大于三分子的聚合物时，交联后制备的漆膜的耐热性能够得到明显改善。
本发明提供的组合物中，所述组合物中的亚氨代噁二嗪二酮结构与所述组合物中的异氰脲酸酯结构的摩尔比可以为0.01：1、0.05：1、0.08：1、0.1：1、0.2：1、0.3：1、0.4：1、0.5：1、0.6：1、0.7：1、0.8：1等任意比值或任意组合的比值区间。
本发明提供的组合物中，所述大于三分子聚合物中的亚氨代噁二嗪二酮结构与所述组合物中的亚氨代噁二嗪二酮结构的摩尔比可以为0.2：1、0.3：1、0.4：1、0.5：1、0.6：1、0.7：1、0.8：1等任意比值或任意组合的比值区间。
本发明提供的组合物中，所述三分子聚合物可以占所述脂肪族多异氰酸酯组合物质量含量的30～75％，例如可以为30％、35％、40％、45％、50％、55％、60％、65％、70％、75％等任意含量值或任意组合的含量值区间。
本发明提供的组合物中，所述脂肪族二异氰酸酯可以为用于制备脂肪族多异氰酸酯的已知任意种类，包括但不限于四亚甲基-1,4-二异氰酸酯、五亚甲基-1,5-二异氰酸酯、六亚甲基-1,6-二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯等。
在一些优选的实施方式中，所述脂肪族二异氰酸酯可以为六亚甲基-1,6-二异氰酸酯或异佛尔酮二异氰酸酯。
本发明提供的所述脂肪族多异氰酸酯组合物的制备方法包括以下步骤：
S1：以脂肪族二异氰酸酯为起始原料，在催化剂A存在下进行反应，获得反应液Ⅰ，其中，所述催化剂A选自四乙基氟化铵、四正丁基氟化铵、十六烷基三甲基氟化铵、四甲基铵三唑盐、四丁基膦三唑盐或四丁基膦苯并三唑盐；
S2：以步骤S1所得的反应液Ⅰ为原料，在催化剂B存在下继续反应，获得反应液Ⅱ,其中，所述催化剂B选自四甲基乙酸铵、十二烷基三甲基辛酸胺、DABCO TMR或N,N,N-三甲基-N-羟丙基甲酸季铵盐；以及
S3：通过薄膜蒸发分离出未反应的脂肪族二异氰酸酯。
本发明提供的制备方法中，在催化剂A存在下，所得的反应液Ⅰ中含有较多的亚氨代噁二嗪二酮结构，而在催化剂B存在下，几乎不产生亚氨代噁二嗪二酮结构，而是使脂肪 族二异氰酸酯进一步形成多聚体，由此可控制所得产物中亚氨代噁二嗪二酮结构的含量和分布，由此得到性能优异的脂肪族多异氰酸酯组合物。而且，本发明提供的制备方法也几乎不产生影响脂肪族多异氰酸酯组合物性质的其他结构或杂质。
本发明提供的制备方法中，亚氨代噁二嗪二酮结构的含量和分布可取决于步骤S1和步骤S2的反应转化率分配。
在一些优选的实施方式中，所述步骤S1中，反应转化率达到1～20％时，终止反应获得所述反应液Ⅰ。
在一些优选的实施方式中，所述步骤S2中，反应转化率达到25～65％时，终止反应获得所述反应液Ⅱ。
本发明提供的制备方法中，所述步骤S1所使用的催化剂A还可以为其它的与四乙基氟化铵、四正丁基氟化铵、十六烷基三甲基氟化铵等具有类似催化性质的氟化季铵盐；还可以为其它的与四甲基铵三唑盐、四丁基膦三唑盐、四丁基膦苯并三唑盐等具有类似催化性质的季铵三唑盐。
本发明提供的制备方法中，所述步骤S2所使用的催化剂B还可以为其它的与四甲基乙酸铵、十二烷基三甲基辛酸胺、DABCO TMR、N,N,N-三甲基-N-羟丙基甲酸季铵盐等具有类似催化性质的羧酸季铵盐。
本发明提供的制备方法中，所述步骤S1和步骤S2中的反应温度可以为55～70℃。
本发明提供的制备方法中，薄膜蒸发的温度可以为120～180℃。
本发明提供的制备方法中，用于终止反应的终止剂可以根据催化剂A、B的种类相应选择，例如，可以为磷酸二正丁酯。
本发明提供的涂料组合物包含以上技术方案任一项所述的脂肪族多异氰酸酯组合物。
本发明提供的涂料组合物中，还可以包含已知的任意辅助成分，包括但不限于丙烯酸系多元醇、聚酯多元醇等。
在一些实施方式中，所述丙烯酸系多元醇选自由以下单体中的一种或多种聚合而成的多元醇：丙烯酸-2-羟基乙酯、丙烯酸-2-羟基丙酯、丙烯酸-2-羟基丁酯、甘油的丙烯酸单酯或甲基丙烯酸单酯、三羟甲基丙烷的丙烯酸单酯或甲基丙烯酸单酯；所述聚酯多元醇为选自丁二酸、己二酸、癸二酸、马来酸酐、邻苯二甲酸酐、间苯二甲酸、对苯二甲酸中的一种或多种羧酸或酸酐与选自乙二醇、丙二醇、二乙二醇、新戊二醇、三羟甲基丙烷、甘 油中的一种或多种多元醇通过缩合反应得到的聚酯多元醇。
本发明提供的涂料组合物中，本发明提供的脂肪族多异氰酸酯组合物还可以与其他来源或性质的多异氰酸酯组合物进行组合使用，以便于调节所得涂料组合物的性能。
本发明提供的涂料组合物可通过现有技术、现有设备进行制备。
本发明提供的脂肪族多异氰酸酯组合物通过特定地控制亚氨代噁二嗪二酮结构的含量和分布，可以同时兼具较低的粘度和较好的交联性，在用于涂料组合物后，能够显著减少溶剂的使用量，更加环境友好，而且还具有更好的漆膜性能，在干燥速度、漆膜硬度、耐溶剂擦拭性能等多个方面都得到了明显的改善。本发明的制备方法工艺简便，条件温和，易于操作和控制，适宜工业规模的生产。
具体实施方式
以下结合具体实施例对本发明的技术方案做进一步详细说明。
本发明的实施例及对比例中，通过凝胶色谱法获得多异氰酸酯组合物中各组分的质量占比，其中的三分子聚合物的质量占比用“TW”表示，TW为凝胶色谱中停留时间为25.25min-26.5min出峰的面积百分比，同时收集三分子聚合物的流动相。
凝胶色谱测试方法为使用LC-20AD/RID-10A，色谱柱为MZ-Gel SDplus 10E3A 5μm(8.0×300mm)、MZ-Gel SDplus 500A 5μm(8.0×300mm)、MZ-Gel SDplus 100A 5μm(8.0×300mm)串联，岛津；流动相：四氢呋喃；流速：1.0mL/min；分析时间：40min，色谱柱温度：35℃。
多异氰酸酯组合物中三分子聚合物的摩尔占比使用“TM”表示，TM＝[TW/(3×异氰酸酯单体分子量)]/组合物中所有组分的摩尔占比之和
组合物中各组分的摩尔占比之和根据各组分通过凝胶色谱法所得的质量占比换算并相加得到。
亚氨代噁二嗪二酮结构摩尔百分比用“A”表示，A＝亚氨代噁二嗪二酮结构/(亚氨代噁二嗪二酮结构+异氰脲酸酯结构)
异氰脲酸酯结构摩尔百分比用“T”表示，T＝异氰脲酸酯结构/(亚氨代噁二嗪二酮结构+异氰脲酸酯结构)
亚氨代噁二嗪二酮结构/异氰脲酸酯结构的摩尔比用“X”表示，则X＝A/T
三分子聚合物中亚氨代噁二嗪二酮结构摩尔百分比用“AT”表示，AT＝三分子亚氨代噁二嗪二酮结构/(三分子亚氨代噁二嗪二酮结构+三分子异氰脲酸酯结构)
A、T和AT的测试方法采用 13C-NMR核磁共振法。所使用的仪器为Bruker 400MHz仪器，样品浓度为50％(CDCl 3溶液)，测试条件为100MHz，松弛时间：4s，扫描次数2000次，以δ＝77.0ppm CDCl 3作为位移参比。
A、T的测试为采集组合物的核磁共振谱图(记为“谱图1”)，AT的测试为采集通过凝胶色谱收集的三分子聚合物组分的核磁共振谱图(记为“谱图2”)，即收集到的三分子聚合物流动相浓缩除去THF后所得的物质。
异氰脲酸酯结构：148.4ppm附近一个吸收峰
亚氨代噁二嗪二酮结构：147.8ppm，144.4ppm，135.2ppm三个吸收峰
A的计算方式为：谱图1中，135.2ppm附近积分值/(148.4ppm附近积分值/3+135.2ppm附近积分值)
T的计算方式如下：谱图1中，(148.4ppm附近积分值/3)/(148.4ppm附近积分值/3+135.2ppm附近积分值)
AT的计算方式为：谱图2中，135.2ppm附近积分值/(148.4ppm附近积分值/3+135.2ppm附近积分值)
大于三分子聚合物中亚氨代噁二嗪二酮结构/组合物中总的亚氨代噁二嗪二酮结构的摩尔比用“Y”表示。
大于三分子聚合物中亚氨代噁二嗪二酮结构/组合物中总的亚氨代噁二嗪二酮结构的摩尔比Y＝(A-TM×AT)/A
本发明的实施例和对比例中，“反应转化率”是指基于起始的脂肪族二异氰酸酯原料的质量，已反应转化的脂肪族二异氰酸酯所占的质量比。所使用的其他试剂如无特别说明均为市售产品，所使用的装置或操作方法如无特别说明，均为本领域常见装置或操作方法。
本发明的测试例中，漆膜性能测试按照如下方法进行：
干燥时间测试：使用直线式干燥时间记录仪，按国标GB/T 1728进行干燥时间读数。
摆杆硬度测试：将喷涂/刮涂好的样板常温放置15～20min，80℃烘烤30min，常温放置 30min后测试进行摆杆硬度测试。
机械性能测试：漆膜刮涂后，常温放置7天，进行铅笔硬度及附着力(十字划格法)测试。
耐乙醇擦拭测试：漆膜刮涂后，在70℃烘烤30min，放置24h后使用耐溶剂擦拭仪进行乙醇擦拭测试。
实施例1-4及对比例1-6脂肪族多异氰酸酯组合物的制备
制备原料及工艺参数如表1所示，通用实验步骤如下：
反应a：5kg脂肪族二异氰酸酯单体置于四口烧瓶中，氮气保护下，升温至50℃，搅拌条件下加入10ml的四正丁基氟化铵(1M THF溶液，购自阿拉丁试剂公司)催化剂，并开始计时。反应的过程中，控制反应温度在55℃至70℃，通过凝胶色谱进行脂肪族二异氰酸酯单体定量，监控反应的转化率。到达规定的转化率时，添加0.01mol磷酸二正丁酯终止剂终止反应a，得到反应液Ⅰ。
反应b：将反应液Ⅰ冷却至50℃，搅拌条件下加入3ml DABCO TMR(购自Evonik公司)催化剂，并开始计时。反应的过程中，控制反应温度在55℃至70℃，通过凝胶色谱进行脂肪族二异氰酸酯单体定量，监控反应的转化率。到达规定的转化率时，添加0.01mol磷酸二正丁酯终止剂终止反应b，得到反应液Ⅱ。
将反应液Ⅱ使用薄膜蒸发，在120-180℃的温度下进行分离，得到浅色多异氰酸酯产品，其组成和粘度如表1所示。
表1实施例及对比例的工艺参数及制得的多异氰酸酯组合物组成
Figure PCTCN2020103277-appb-000004
Figure PCTCN2020103277-appb-000005
(1)IPDI多异氰酸酯的粘度为基于70％乙酸丁酯溶液测得。
测试例
使用实施例1-4及对比例1-6制得的脂肪族多异氰酸酯组合物制备涂料组合物并进行涂膜评价。
HDI型异氰酸酯涂料组合物涂膜评价配方：采用羟丙树脂(AC1100B)搭配上述实施例及对比例制备的HDI型脂肪族多异氰酸酯组合物，异氰酸酯基团与羟基基团摩尔比为1.1：1，涂料固含40％，溶剂为乙酸丁酯和二甲苯，质量比为1：1。评价结果如表2所示。
IPDI型异氰酸酯涂料组合物涂膜评价配方：采用羟丙树脂(AC1100B)搭配上述实施例及对比例制备的IPDI型脂肪族多异氰酸酯组合物及市售HDI三聚体产品WANNATE HT-100，IPDI型脂肪族多异氰酸酯组合物与WANNATE HT-100质量比为1：5，总异氰酸酯基团与羟基基团摩尔比为1.1：1，涂料固含40％，溶剂为乙酸丁酯和二甲苯，质量比为1：1。评价结果如表3所示。
表2基于HDI型多异氰酸酯组合物的涂料组合物性能评价
Figure PCTCN2020103277-appb-000006
Figure PCTCN2020103277-appb-000007
表3基于IPDI型多异氰酸酯组合物的涂料组合物性能评价
Figure PCTCN2020103277-appb-000008
由上述对比例1-3、6可以看出，当亚氨代噁二嗪二酮结构的含量较少时，多异氰酸酯组合物的粘度较高，而由上述对比例4-5可以看出，当亚氨代噁二嗪二酮结构达到一定数量，但未更多地分布于大于三分子聚合物中时，虽然能够降低多异氰酸酯组合物的粘度，但用于涂料组合物后的漆膜性能较差。
通过上述实施例和测试例可以看出，本发明提供的脂肪族多异氰酸酯组合物通过控制亚氨代噁二嗪二酮结构的含量和分布，能够具有更低的粘度，用于涂料组合物后，制备的漆膜具有更快的干燥速度、更优的漆膜硬度及耐溶剂擦拭性能，综合性能得到了显著提升，因而非常具备应用前景。
除非特别限定，本发明所用术语均为本领域技术人员通常理解的含义。
本发明所描述的实施方式仅出于示例性目的，并非用以限制本发明的保护范围，本领域技术人员可在本发明的范围内作出各种其他替换、改变和改进，因而，本发明不限于上述实施方式，而仅由权利要求限定。

Claims (9)

  1. 一种脂肪族多异氰酸酯组合物，其以脂肪族二异氰酸酯为起始原料制得，由所述脂肪族二异氰酸酯形成的三分子聚合物和大于三分子聚合物组成，所述组合物中具有亚氨代噁二嗪二酮结构以及异氰脲酸酯结构，其特征在于，所述组合物中的亚氨代噁二嗪二酮结构与所述组合物中的异氰脲酸酯结构的摩尔比为0.01～0.8：1，且所述大于三分子聚合物中的亚氨代噁二嗪二酮结构与所述组合物中的亚氨代噁二嗪二酮结构的摩尔比为0.2～0.8：1。
  2. 根据权利要求1所述的脂肪族多异氰酸酯组合物，其特征在于，所述三分子聚合物占所述脂肪族多异氰酸酯组合物质量含量的30～75％。
  3. 根据权利要求1或2所述的脂肪族多异氰酸酯组合物，其特征在于，所述脂肪族二异氰酸酯选自四亚甲基-1,4-二异氰酸酯、五亚甲基-1,5-二异氰酸酯、六亚甲基-1,6-二异氰酸酯、异佛尔酮二异氰酸酯或二环己基甲烷二异氰酸酯。
  4. 根据权利要求3所述的脂肪族多异氰酸酯组合物，其特征在于，所述脂肪族二异氰酸酯选自六亚甲基-1,6-二异氰酸酯或异佛尔酮二异氰酸酯。
  5. 权利要求1-4任一项所述的脂肪族多异氰酸酯组合物的制备方法，其特征在于，包括以下步骤：
    S1：以脂肪族二异氰酸酯为起始原料，在催化剂A存在下进行反应，获得反应液Ⅰ，其中，所述催化剂A选自四乙基氟化铵、四正丁基氟化铵、十六烷基三甲基氟化铵、四甲基铵三唑盐、四丁基膦三唑盐或四丁基膦苯并三唑盐；
    S2：以步骤S1所得的反应液Ⅰ为原料，在催化剂B存在下继续反应，获得反应液Ⅱ,其中，所述催化剂B选自四甲基乙酸铵、十二烷基三甲基辛酸胺、DABCO TMR或N,N,N-三甲基-N-羟丙基甲酸季铵盐；以及
    S3：通过薄膜蒸发分离出未反应的脂肪族二异氰酸酯。
  6. 根据权利要求5所述的制备方法，其特征在于，所述步骤S1中，反应转化率达到1～20％时，终止反应获得所述反应液Ⅰ。
  7. 根据权利要求5或6所述的制备方法，其特征在于，所述步骤S2中，反应转化率达到25～65％时，终止反应获得所述反应液Ⅱ。
  8. 根据权利要求5-7中任一项所述的制备方法，其特征在于，所述步骤S1和步骤S2中的反应温度为55～70℃。
  9. 一种涂料组合物，其特征在于，包含权利要求1-4任一项所述的脂肪族多异氰酸酯组合物。
PCT/CN2020/103277 2019-11-08 2020-07-21 脂肪族多异氰酸酯组合物、其制备方法及涂料组合物 WO2021088416A1 (zh)

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