A uretonimine composition, a polyisocyanate composition, and a method for producing and using the same

Abstract

The present application provides a kind of uretonimine composition, polyisocyanate composition and its preparation method and application, the uretonimine composition includes the combination of uretonimine A with formula I and uretonimine B with formula II structure;With the collocation of uretonimine A and uretonimine B, the obtained uretonimine composition can reduce the effect of the viscosity of polyisocyanate composition when added to polyisocyanate composition, and can also meet good compatibility, so that the polyisocyanate composition can be widely used in the preparation of paint film excellent paint composition.

Description

Technical Field

[0001] This invention belongs to the field of isocyanate technology, specifically relating to a urea carbamate composition, a polyisocyanate composition, its preparation method and application. Background Technology

[0002] Aliphatic polyisocyanates containing isocyanurate structures possess excellent weather resistance, chemical resistance, and heat resistance, making them widely used in high-end applications such as original equipment automotive paints and refinish paints, especially as clear coats. In recent years, due to increasingly stringent environmental protection requirements, and in order to reduce the use of organic solvents in coating compositions, polyisocyanates used as curing agents have gradually shifted towards lower viscosity.

[0003] Currently disclosed methods for preparing low-viscosity polyisocyanate compositions containing isocyanurate structures mainly include reducing reaction conversion rate and introducing modifying components. US4801663A discloses a low-viscosity polyisocyanate composition in which the proportion of isocyanurate monocyclic polymer is as high as 70-75%, but its reaction conversion rate can only reach 12-21%, and the overall yield of the reaction is significantly reduced; however, this method requires the removal of a large amount of unreacted monomers from the final reaction product, which greatly increases the production cost of this method.

[0004] US5354834A achieves a reduction in product viscosity by controlling the content of isocyanurate trimer to be below 60% and the content of urea diketone dimer to be above 10% in the composition. Increasing the content of urea diketone dimer is beneficial to reducing the viscosity of the composition. However, urea diketone dimer has a linear structure and poor crosslinking, thermal stability and compatibility, which is detrimental to the hardness, weather resistance and appearance of the paint film. In addition, there is a problem of increased monomer content during storage.

[0005] CN1757639A discloses a method for preparing low-viscosity polyisocyanates. This method uses quaternary ammonium salts or phosphonium salts of polyfluoric acid as catalysts to prepare polyisocyanates containing iminooxadiazine dione groups, which can reduce the viscosity of polyisocyanate compositions. However, the iminooxadiazine dione structure has poor stability, and the introduction of fluorine makes this method not safe and environmentally friendly.

[0006] CN101291970A discloses a method for reducing the viscosity of polyisocyanate compositions by obtaining a urea-containing formate structure through monohydric alcohol modification. However, the urea-containing formate structure obtained by monohydric alcohol modification has poor compatibility, and the appearance and gloss of the resulting paint film are insufficient when applied to coating compositions.

[0007] As can be seen from the above, it is difficult for the polyisocyanate compositions provided in the current technology to simultaneously guarantee both low viscosity and good compatibility.

[0008] Therefore, developing a urethane composition that can combine low viscosity and excellent compatibility with polyisocyanate compositions is a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0009] To address the shortcomings of existing technologies, the present invention aims to provide a urea-formaldehyde ester composition, a polyisocyanate composition, a preparation method thereof, and its application. By limiting the urea-formaldehyde ester composition to include a combination of urea-formaldehyde ester A and urea-formaldehyde ester B, the polyisocyanate composition containing the urea-formaldehyde ester composition can not only have a lower viscosity but also better compatibility. When applied to coating compositions, it can ensure that the formed coating film has good gloss and excellent appearance.

[0010] To achieve this objective, the present invention adopts the following technical solution:

[0011] In a first aspect, the present invention provides a urethane composition comprising a combination of urethane A and urethane B;

[0012] The structure of the urethane ester A is shown in Formula I:

[0013]

[0014] The structure of the urethane ester B is shown in Formula II:

[0015]

[0016] R1, R3, and R4 are each independently selected from C2-C14 chain or cyclic alkylene groups (e.g., C3, C4, C5, C6, C7, C8, C9, C10, or C12 alkylene groups), and R2 is selected from C2-C14 chain or cyclic alkyl groups (e.g., C3, C4, C5, C6, C7, C8, C9, C10, or C12 alkyl groups).

[0017] The urea-formaldehyde ester composition provided by the present invention comprises a combination of urea-formaldehyde ester A having the structure shown in Formula I and urea-formaldehyde ester B having the structure shown in Formula II. By limiting the urea-formaldehyde ester composition to include the above two components, the polyisocyanate composition containing it can have a lower viscosity while satisfying good compatibility, thereby it can be widely used in the preparation of coating compositions with good film performance.

[0018] Preferably, the mass ratio of the urea ester A to the urea ester B is (0.01 to 10):1, for example, 0.05:1, 0.1:1, 0.5:1, 1:1, 2:1, 4:1, 6:1 or 8:1.

[0019] As a preferred technical solution of the present invention, a urea-formate composition composed of urea-formate A and urea-formate B in a mass ratio of (0.01 to 10):1 can further improve the overall performance of the polyisocyanate composition containing it. On the one hand, when the mass ratio of urea-formate A and urea-formate B is lower than the above-mentioned range, the urea-formate composition formed by the two will have a poor effect on adjusting the viscosity of the polyisocyanate composition and cannot effectively reduce the viscosity of the polyisocyanate composition. On the other hand, when the mass ratio of urea-formate A and urea-formate B is higher than the above-mentioned range, adding the urea-formate composition formed by the two to the polyisocyanate composition will tend to reduce the compatibility of the polyisocyanate composition with the solvent.

[0020] Preferably, the raw materials for preparing urethane ester A include diisocyanate A and a monohydric alcohol.

[0021] The monohydric alcohol has the structure R2-OH, and the diisocyanate A has the structure OCN-R1-NCO. R1 and R2 in Formula I have the same range of values.

[0022] Preferably, the monohydric alcohol comprises a monohydric alcohol having 2 to 10 carbon atoms (e.g., 2, 4, 6 or 8), and more preferably an aliphatic monohydric alcohol having 2 to 10 carbon atoms.

[0023] Preferably, the aliphatic monohydric alcohol includes any one or a combination of at least two of methanol, ethanol, propanol, n-butanol, hexanol, isobutanol, or 2-ethylhexanol.

[0024] Preferably, the raw materials for preparing the urea-formate B include diisocyanate B and a diol.

[0025] The structure of the diol is HO-R3-OH, and the structure of the diisocyanate B is OCN-R4-NCO. R3 and R4 have the same range of values ​​as R3 and R4 in Formula ⅠI.

[0026] Preferably, the diol comprises a diol having 2 to 12 carbon atoms (e.g., 3, 5, 7, 9 or 11), and more preferably an aliphatic diol having 2 to 12 carbon atoms, wherein the structure of the diol is HO-R3-OH, and R3 is selected from C2-C14 alkylene groups.

[0027] Preferably, the aliphatic diol includes any one or a combination of at least two of the following: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, or 2,2-diethyl-1,3-propanediol.

[0028] Preferably, the diisocyanate A and diisocyanate B each independently comprise any one or a combination of at least two of tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or lysine diisocyanate, and more preferably pentamethylene diisocyanate (PDI) and / or hexamethylene diisocyanate (HDI).

[0029] In a second aspect, the present invention provides a method for preparing a urethane composition as described in the first aspect, the preparation method comprising method A or method B;

[0030] Method A includes: reacting diisocyanate and monohydric alcohol, adding dihydric alcohol to react, and obtaining the urea carbamate composition;

[0031] Method B includes the following steps:

[0032] (B1) Diisocyanate A is reacted with a monohydric alcohol to obtain urethane A; diisocyanate B is reacted with a dihydric alcohol to obtain urethane B;

[0033] (B2) Mix urethane A and urethane B obtained in step (B1) to obtain the urethane composition.

[0034] It should be noted that in Method A above, the diisocyanate includes diisocyanate A and / or diisocyanate B, and the same concepts mentioned below have the same meaning.

[0035] It should also be noted that Method A or Method B provided by the present invention are merely examples of methods for preparing urethane ester compositions and are not intended to limit their composition or structure. In Method A and Method B, the ratio of urethane ester A and urethane ester B can be controlled by adjusting the amounts of monohydric alcohol, dihydric alcohol, and isocyanate, as well as by adjusting reaction time and temperature. After the reaction in Method A and Method B is completed, steps for removing unreacted monomers and / or removing byproducts can also be included. The specific methods for removing byproducts and / or unreacted monomers are all conventional methods and can be selected according to specific needs.

[0036] Preferably, in method A, the mass of the monohydric alcohol is 0.05% to 5%, for example, 0.1%, 0.5%, 1%, 2%, 3% or 4%, based on the mass of the diisocyanate being 100%.

[0037] Preferably, in method A, the reaction time for the diisocyanate and the monohydric alcohol is 2 to 5 hours, such as 2.3 hours, 2.6 hours, 2.9 hours, 3.2 hours, 3.5 hours, 3.8 hours, 4.1 hours, 4.4 hours, or 4.7 hours.

[0038] Preferably, in method A, the reaction temperature for the reaction between the diisocyanate and the monohydric alcohol is 90–120°C, for example, 95°C, 100°C, 105°C, 110°C, or 115°C.

[0039] As a preferred technical solution of the present invention, the reaction conditions of 90-120°C are more conducive to the formation of urethane A.

[0040] Preferably, in method A, the mass of the diol is 0.01 to 5% based on the mass of the diisocyanate being 100%, for example, 0.1%, 0.5%, 1%, 2%, 3%, or 4%.

[0041] Preferably, in method A, the reaction temperature for adding the diol is 50–80°C, for example, 55°C, 60°C, 65°C, 70°C, or 75°C.

[0042] Preferably, in method A, the reaction with the addition of diol is terminated when the conversion rate of diisocyanate is 30-60% (e.g., 35%, 40%, 45%, 50% or 55%).

[0043] Preferably, in method B, the reaction temperature for reacting the diisocyanate and the monohydric alcohol is 80–120°C, such as 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, or 115°C.

[0044] Preferably, in method B, the reaction time for reacting the diisocyanate and the monohydric alcohol is 0.5 to 2 hours, for example, 0.7 hours, 0.9 hours, 1.1 hours, 1.3 hours, 1.5 hours, 1.7 hours, or 1.9 hours.

[0045] Preferably, in method B, the reaction temperature for reacting the diisocyanate and the diol is 80–120°C, such as 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, or 115°C.

[0046] Preferably, in method B, the reaction time for reacting the diisocyanate and the diol is 0.5 to 2 hours, for example, 0.7 hours, 0.9 hours, 1.1 hours, 1.3 hours, 1.5 hours, 1.7 hours, or 1.9 hours.

[0047] Preferably, in method B, the reaction of diisocyanate and monohydric alcohol and the reaction of diisocyanate and dihydric alcohol are both carried out under the catalytic conditions of a urea-formylation catalyst.

[0048] Preferably, the ureocarboxylation catalyst comprises bismuth 2-ethylhexanoate.

[0049] Thirdly, the present invention provides a polyisocyanate composition comprising a combination of a urea carbamate composition as described in the first aspect and an isocyanate polymer.

[0050] Preferably, the molar ratio of urea ester groups to isocyanurate groups in the polyisocyanate composition is (0.01-3):1, for example, 0.05:1, 0.1:1, 0.5:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1 or 2.8:1, etc.

[0051] As a preferred embodiment of the present invention, the molar ratio of urea ester groups to isocyanurate groups in the polyisocyanate composition is limited to (0.01-3):1, which enables the polyisocyanate composition to have both low viscosity and good compatibility, as well as good crosslinking properties.

[0052] In this invention, the isocyanurate group refers to the functional group contained in the isocyanate trimer, having the structure shown in Formula III, and the urea carbamate group refers to the functional group formed by the hydroxyl group and the isocyanate group, having the structure shown in Formula VI.

[0053]

[0054] In this context, the dashed lines represent the connecting bonds of functional groups.

[0055] Preferably, the isocyanate polymer comprises an isocyanate trimer.

[0056] Fourthly, the present invention provides a method for preparing a polyisocyanate composition, the preparation method comprising method C or method D;

[0057] Method C includes: mixing a urea carbamate composition and an isocyanate polymer to obtain the polyisocyanate composition;

[0058] Method D includes the following steps:

[0059] (D1) The diisocyanate and the monohydric alcohol were reacted to obtain a reaction solution containing urethane A;

[0060] (D2) The reaction solution containing urethane A obtained in step (D1), the diol and the catalyst are reacted, and a terminator is added to obtain the polyisocyanate composition.

[0061] In this invention, method D is preferred for preparing the polyisocyanate composition. Method D can directly produce a polyisocyanate composition containing a urea-formate composition and an isocyanate polymer, which is more suitable for industrial production. In method D, diisocyanate and monohydric alcohol are first reacted to generate a reaction solution containing urea-formate A. Then, by adding a certain amount of dihydric alcohol, the system continues to react under the action of a catalyst to form a urea-formate B structure. By controlling the amount of monohydric alcohol in step (D1) and the amount of dihydric alcohol added in step (D2), as well as by controlling the reaction time and temperature, the ratio of urea-formate A, urea-formate B, and the isocyanate polymer can be controlled, thereby reducing the viscosity of the composition and improving the compatibility of the final isocyanate composition.

[0062] Preferably, the mass of the catalyst in step (2) is 10 to 1000 ppm, for example, 50 ppm, 100 ppm, 200 ppm, 400 ppm, 600 ppm or 800 ppm, based on the mass of the diisocyanate in step (1) being 100%.

[0063] Preferably, the catalyst comprises any one or at least a combination of two of the following: quaternary ammonium catalysts, silazane catalysts, alkylphosphine catalysts, tertiary amine catalysts, or manniene base catalysts.

[0064] Preferably, the quaternary ammonium catalyst includes quaternary ammonium base catalysts and / or quaternary ammonium salt catalysts, more preferably any one or at least two combinations of choline hydroxide, trimethylhydroxyethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, 1-adamantylammonium hydroxide, hexamethylbisammonium hydroxide, tetramethylammonium, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium decanoate, trimethylhydroxypropylammonium formate, trimethylhydroxypropylammonium acetate, trimethylhydroxypropylammonium octanoate, trimethylhydroxypropylammonium decanoate, trimethylhydroxyethylammonium formate, trimethylhydroxyethylammonium acetate, or trimethylhydroxyethylammonium decanoate, and even more preferably tetraethylammonium hydroxide and / or trimethylhydroxypropylammonium octanoate.

[0065] Preferably, the silazane catalyst comprises hexamethyldisilazane and / or heptamethyldisilazane.

[0066] Preferably, the alkylphosphine catalyst includes tributylphosphine and / or triphenylphosphine.

[0067] Preferably, the tertiary amine catalyst includes triethylamine.

[0068] Preferably, the manniene base catalyst includes DMP-30.

[0069] Preferably, the terminating agent comprises an acidic substance, and more preferably any one or a combination of at least two of phosphoric acid, formic acid, benzoic acid, benzoyl chloride or diisooctyl phosphate.

[0070] Preferably, the addition of the terminator further includes a step of removing unreacted diisocyanate.

[0071] Preferably, the method for removing unreacted diisocyanate includes any one or a combination of at least two of the following: thin-film evaporation, falling-film evaporation, short-path evaporation, or vacuum distillation; more preferably, a two-stage thin-film evaporation method.

[0072] Preferably, the temperature of the secondary thin-film evaporation method is 120-180°C, such as 125°C, 130°C, 135°C, 140°C, 150°C, 160°C or 170°C.

[0073] Fifthly, the present invention provides a coating composition comprising a polyisocyanate composition as described in the third aspect and a polymeric polyol.

[0074] Preferably, the molar ratio of isocyanate groups to hydroxyl groups in the polyisocyanate composition is (1 to 1.5):1, for example, 1.05:1, 1.1:1, 1.15:1, 1.2:1, 1.25:1, 1.3:1, 1.35:1, 1.4:1 or 1.45:1, etc.

[0075] Preferably, the polymeric polyol comprises acrylic polyols and / or polyester polyols.

[0076] Preferably, the raw materials for preparing the acrylic polyol include any one or a combination of at least two of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, or 2-hydroxybutyl acrylate.

[0077] Preferably, the raw materials for preparing the polyester polyol include acid monomers and alcohol monomers.

[0078] Preferably, the acid monomers include any one or a combination of at least two of succinic acid, adipic acid, sebacic acid, or maleic anhydride.

[0079] Preferably, the alcohol monomer includes any one or a combination of at least two of ethylene glycol, propylene glycol, diethylene glycol, or neopentyl glycol.

[0080] Preferably, the number average molecular weight of the polymer polyol is 2000-8000, such as 3000, 4000, 5000, 6000 or 7000.

[0081] As a preferred technical solution of the present invention, the present invention preferably uses polymeric polyols with a number average molecular weight of 2000 to 8000. When the number average molecular weight of the polymeric polyol is lower than 2000, its crosslinking degree is poor when applied to the coating composition. When the number average molecular weight of the polymeric polyol is higher than 8000, its film compatibility is poor when applied to the coating composition, which further affects the gloss and texture of the film. It is preferred that the number average molecular weight of the polymeric polyol is 2000 to 8000, so that the coating composition can simultaneously ensure that it has both excellent crosslinking degree and compatibility.

[0082] Compared with the prior art, the present invention has the following beneficial effects:

[0083] The urea-formaldehyde ester composition provided by the present invention comprises a combination of urea-formaldehyde ester A having the structure shown in Formula I and urea-formaldehyde ester B having the structure shown in Formula II. By selecting the combination of urea-formaldehyde ester A having the structure shown in Formula I and urea-formaldehyde ester B having the structure shown in Formula II, the polyisocyanate composition containing it can have a lower viscosity and good compatibility. When used in coating compositions, it can significantly reduce the amount of solvent used, making it more environmentally friendly, and also has better film performance, with significant improvements in gloss and appearance. Detailed Implementation

[0084] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0085] The raw material information involved in the specific embodiments of this invention is shown in Table 1:

[0086] Table 1

[0087] raw material Manufacturer, Brand HDI Wanhua Chemical Group Co., Ltd. PDI Wanhua Chemical Group Co., Ltd. N,N,N-Trimethylbenzylammonium hydroxide Aladdin Isooctyl alcohol Aladdin 1,6-Hexanediol Aladdin

[0088] Example 1

[0089] A urethane composition comprising urethane A and urethane B in a mass ratio of 0.1:1, wherein the structure of urethane A is as follows:

[0090] The structure of urethane B is as follows:

[0091] The preparation method of the urethane ester composition provided in this embodiment includes the following steps:

[0092] (1) 1000g of HDI, 10g of isooctyl alcohol and 0.1g of bismuth 2-ethylhexanoate were reacted at 110℃ for 90min to remove unreacted monomers and obtain urethane ester A; 1000g of HDI, 4g of 1,6-hexanediol and 0.1g of bismuth 2-ethylhexanoate were reacted at 110℃ for 90min to remove unreacted monomers and obtain urethane ester B;

[0093] (2) Mix urethane A and urethane B obtained in step (1) to obtain the urethane composition.

[0094] Characterization data: The viscosity of the urethane composition was determined to be 3200 cP using a Brookfield RC / S rheometer.

[0095] In addition to Example 1 above, the present invention also provides the following specific application examples for directly preparing polyisocyanate compositions containing urea carbamate compositions;

[0096] The methods for determining the reaction conversion rate, free diisocyanate monomer content, molar ratio of urea ester groups to isocyanurate groups, and area ratio of urea ester A and urea ester B in liquid chromatography in the application examples are as follows:

[0097] (1) Reaction conversion rate: refers to the mass ratio of diisocyanate to diisocyanate that has been converted from the initial diisocyanate raw material. The conversion rate is monitored by quantifying the diisocyanate monomers using gel chromatography. The test conditions are as follows: the gel chromatography instrument is LC-20AD / RID-10A, the chromatographic columns are MZ-Gel SDplus 10E3A 5μm (8.0×300mm), MZ-Gel SDplus 500A 5μm (8.0×300mm), and MZ-Gel SDplus 100A 5μm (8.0×300mm) in series, Shimadzu; mobile phase: tetrahydrofuran; flow rate: 1.0mL / min; analysis time: 40min; column temperature: 35℃.

[0098] (2) Content of free diisocyanate monomer: Based on the method of GB / T18583-2008, the content of residual diisocyanate monomer in the reaction system was determined by Agilent GC-7890B gas chromatograph manufactured by Agilent.

[0099] (3) Molar ratio of urea ester group to isocyanurate group: quantified by composition 13 The CNMR test is used to determine the value, and the specific test conditions are as follows: 13 C-NMR equipment: AVANCE600 (Bruker); BBO probe (Bruker); Sample concentration: 30wt%; Resonance frequency: 150MHz; Shift reference: 77.0ppm (CDCl3); Pulse program: zgig30; Spectral width: 240ppm; Spectral center: 100ppm; Isocyanurate group: integral value near 148.5ppm / 3; Urea carbamate group: integral value near 154ppm / 1.

[0100] (4) Area ratio of urethane A and urethane B in liquid chromatography (mass ratio of the two): The terminal isocyanate groups of urethane A and urethane B in the polyisocyanate composition were urethane-urethaned with methanol and analyzed by liquid chromatography-mass spectrometry (LC / MS) to calculate the area ratio of urethane A and urethane B in liquid chromatography.

[0101] The determination method includes: ① Sample preparation: Weigh 100 mg of the polyisocyanate composition, add methanol to prepare a solution of 10 mg / mL, and then let it stand for 2 days to allow the existing isocyanate groups to react completely with the methanol; ② The test is performed using an UPLC-HRMS device, Ultimate 3000-Thermo Q Exactive Focus; chromatographic column: Agilent Extend C18RRHD 2.1×100mm 1.8um; column temperature: 40℃; detection: 220nm; flow rate: 0.3mL / min; scan range: 100-21500m / z; mobile phase: A: pure water (0.05% formic acid), B: pure acetonitrile (0.05% formic acid).

[0102] Application Examples 1-11

[0103] A polyisocyanate composition comprising a urethane composition and an isocyanate polymer, wherein the urethane composition comprises a combination of urethane A and urethane B;

[0104] The structure of the urethane A is as follows:

[0105] The structure of the urethane ester B is as follows:

[0106] The preparation method of the polyisocyanate composition includes the following steps:

[0107] (1) Add 1000g of diisocyanate and a certain amount of isooctyl alcohol to a 2L four-necked flask, heat to 100℃ under nitrogen protection, and react for 4h to obtain a reaction solution containing urethane A.

[0108] (2) Cool the above reaction solution containing urethane A to 65°C, then add a certain amount of 1,6-hexanediol, and add 0.2g of 20% N,N,N-trimethylbenzylammonium hydroxide isooctyl alcohol solution under stirring. Start timing and control the reaction temperature at 65-70°C. When the conversion rate of diisocyanate reaches 45%, add 0.06g of dibutyl phosphate to terminate the reaction and obtain the reaction solution.

[0109] (3) Using a thin-film evaporator, the above reaction solution was distilled twice at 150°C and 30Pa to obtain a polyisocyanate composition with a diisocyanate content of less than 0.2%.

[0110] The types, amounts, and proportions of substances involved in the polyisocyanate compositions provided in Application Examples 1 to 11 above are shown in Table 2 below:

[0111] Table 2

[0112]

[0113] It should be noted that the amount of isooctanol in Table 2 refers only to the amount of isooctanol added in step (1).

[0114] Application Example 12

[0115] A polyisocyanate composition, which differs from Application Example 4 only in that PDI is used instead of HDI, while the other substances, parameters and preparation methods are the same as in Application Example 1;

[0116] In the polyisocyanate composition obtained by Application Example 12, the molar ratio of urethane and isocyanurate groups is 0.78:1, and the mass ratio of urethane A and urethane B contained is 1.68:1.

[0117] The structure of the urethane A is as follows:

[0118] The structure of the urethane ester B is as follows:

[0119] Comparative Application Example 1

[0120] A method for preparing an isocyanate polymer includes: adding 1000g of HDI to a 2L four-necked flask, controlling the system temperature at 65°C, adding 0.2g of a 20% N,N,N-trimethylbenzylammonium hydroxide isooctanol solution under stirring, starting the timer, controlling the reaction temperature at 70°C, and adding 0.06g of dibutyl phosphate to terminate the reaction when the conversion rate of diisocyanate reaches 45%, thereby obtaining the isocyanate polymer.

[0121] Comparative Application Example 2

[0122] An isocyanate polymer, the polyisocyanate composition comprising urethane and isocyanate polymer, wherein the molar ratio of urethane groups to isocyanurate groups in the polyisocyanate composition is 0.02:1;

[0123] The preparation method of the polyisocyanate composition includes the following steps:

[0124] (1) Add 1000g of HDI and 10g of 1,6-hexanediol to a 2L four-necked flask, control the system temperature at 65℃, add 0.2g of 20% N,N,N-trimethylbenzylammonium hydroxide isooctyl alcohol solution under stirring, and start timing. Control the reaction temperature at 65-70℃. When the reaction conversion rate reaches 45%, add 0.06g of dibutyl phosphate to terminate the reaction and obtain the reaction solution.

[0125] (2) Using a thin-film evaporator, the above reaction solution was distilled twice at 150°C and 30Pa to obtain a polyisocyanate composition with a diisocyanate content of less than 0.2%.

[0126] Comparative Application Example 3

[0127] A polyisocyanate composition comprising urea carbamate and isocyanate polymer, wherein the molar ratio of urea carbamate groups to isocyanurate groups in the polyisocyanate composition is 0.02:1;

[0128] The preparation method of the polyisocyanate composition includes the following steps:

[0129] (1) Add 1000g of HDI and 10g of isooctanol to a 2L four-necked flask, heat to 65℃ under nitrogen protection, add 0.2g of 20% N,N,N-trimethylbenzylammonium hydroxide isooctanol solution under stirring, and start timing. Control the reaction temperature at 65-70℃. When the reaction conversion rate reaches 45%, add 0.06g of dibutyl phosphate to terminate the reaction and obtain the reaction solution.

[0130] (2) Using a thin-film evaporator, the above reaction solution was distilled twice at 150°C and 30Pa to obtain a polyisocyanate composition with a diisocyanate content of less than 0.2%.

[0131] Performance testing:

[0132] (1) Testing of polyisocyanate compositions:

[0133] ① Viscosity: Measured using a Brookfield RC / S rheometer, rotor model CC-40, constant temperature water bath, temperature controlled at 25±0.1℃, shear rate 25S. -1 ~250S -1 .

[0134] ②NCO content: determined according to the test method provided in standard GB / T 12009.4.

[0135] The polyisocyanate compositions provided in Case 1-12 and Comparative Application Examples 1-3 were tested according to the above test methods. The test results are shown in Table 3.

[0136] Table 3

[0137] Viscosity / mPa·s NCO content % Application Example 1 2230 22.1 Application Example 2 2100 22.0 Application Example 3 1880 21.9 Application Example 4 1450 21.4 Application Example 5 986 21.2 Application Example 6 1548 21.8 Application Example 7 1460 21.5 Application Example 8 2430 22.2 Application Example 9 756 20.8 Application Example 10 1642 21.3 Application Example 11 2620 21.9 Application Example 12 1860 21.5 Comparative Application Example 1 4160 22.4 Comparative Application Example 2 4380 22.3 Comparative Application Example 3 1680 21.3

[0138] (2) Testing of coating compositions:

[0139] ① Ethanol wiping resistance: A coating was prepared by mixing hydroxypropyl resin (AC1100B, Tongde resin) and polyisocyanate composition. The raw materials were added according to the molar ratio of isocyanate groups to hydroxyl groups of 1.1:1. The solid content of the coating was 40%, and the solvent was butyl acetate and xylene in a mass ratio of 1:1. After the paint film was scraped, it was baked at 70℃ for 30 min and left for 24 h. Then, an ethanol wiping test was performed using a solvent resistance wiping instrument, and the number of wiping resistances was recorded.

[0140] ② Appearance and gloss of the coating:

[0141] Sample Preparation: Acrylic polyol Ac-1 and the aforementioned polyisocyanate composition were mixed in a 1:1 molar ratio of isocyanate groups to hydroxyl groups. The mixture was then prepared with SOLVESSO#100 (trade name, an aromatic solvent manufactured by ExxonMobil) to a solid content of 55%, thus preparing the coating composition. The coating was then sprayed onto ABS boards (acrylonitrile-butadiene-styrene resin, black, 150×75mm). After drying, the film thickness was 50μm. The film was then calcined at 60°C for 30 min and allowed to stand at 23°C and 50% humidity for one week to form a coating film on the ABS board, which served as the sample for testing.

[0142] Coating appearance (sharpness and surface smoothness): Measurements were taken along the long side of the ABS sheet using a digital oscilloscope, "Wave Scan DOI" (manufactured by BYK Gardner). The "Wave Scan DOI" is configured as follows: a laser point source illuminates the film at a 60° angle relative to the perpendicular from the film surface; a detector receives reflected light at the same angle on the opposite side of the perpendicular. This device moves the laser point source across the film surface and scans it, measuring the brightness of the reflected light point-by-point at predetermined intervals, thus detecting the optical profile of the film surface. The detected optical profile is then subjected to spectral analysis using a filter to analyze the surface structure. Evaluation was performed using the values ​​of the Wb region (wavelength 0.3–1.0 mm) and the Wc region (wavelength 1.0–3.0 mm) of the coating. The measured value was the arithmetic mean of three measurements. Wb and Wc are indicators of coating appearance; Wb represents the sharpness of the coating, and Wc represents its smoothness. Lower values ​​are considered better.

[0143] Gloss of the coating: The gloss of the coating at 60° was measured using “UGV-6P” (manufactured by Suga Test Instruments Co., Ltd.).

[0144] The test samples obtained from test cases 1-12 and comparative application examples 1-3 were tested according to the above test method. The test results are shown in Table 4.

[0145] Table 4

[0146]

[0147] As can be seen from the data in Tables 3 and 4, the polyisocyanate composition containing the urea-formate composition provided by the present invention has a low viscosity and exhibits excellent ethanol scrub resistance, low sharpness and smoothness after coating formation, as well as high film gloss. Specifically, when the mass ratio of urea-formate A to urea-formate B in the polyisocyanate composition is in the range of (0.01 to 10):1, the viscosity of the polyisocyanate is 986 to 2230 mPa·s, the NCO content is 21.2 to 22.1%, the number of ethanol scrub tests after coating formation is as high as 264 to 368, the sharpness is 0.6 to 0.7, the smoothness is 0.15 to 0.7, and the gloss is 72 to 76%.

[0148] Comparing the data from Application Example 1 and Comparative Application Examples 1-3, it can be seen that the polyisocyanate combinations that do not contain urethane A and urethane B (Comparative Application Example 1) and those that only do not contain urethane A (Comparative Application Example 2) have excessively high viscosity, resulting in poor appearance and low gloss after film formation; while the polyisocyanate composition that only does not contain the urethane B structure (Comparative Application Example 3) has poor ethanol scrubbing resistance after film formation.

[0149] Further comparison of the data from Application 1 and Application Examples 8-11 also shows that when the mass ratio of urethane A to urethane B in the polyisocyanate composition is not within the preferred range defined in this invention, it will also affect the performance after the coating is formed.

[0150] The applicant declares that this invention illustrates a urea-formaldehyde ester composition, a polyisocyanate composition, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the products of this invention, additions of auxiliary components, and selection of specific methods, all fall within the protection and disclosure scope of this invention.

Claims

1. A polyisocyanate composition, characterized in that, The polyisocyanate composition comprises a combination of a urea carbamate composition and an isocyanate polymer; The urethane composition comprises a combination of urethane A and urethane B; The structure of the urethane ester A is shown in Formula I: Formula I; The structure of the urethane ester B is shown in Formula II: Formula I; R1, R3 and R4 are each independently selected from C2-C14 chain or cyclic alkylene groups, and R2 is selected from C2-C14 chain or cyclic alkyl groups. The mass ratio of urethane A to urethane B is (0.01~0.15):1; The molar ratio of urea-formate groups to isocyanurate groups in the polyisocyanate composition is (0.01~0.12):

1.

2. The polyisocyanate composition according to claim 1, characterized in that, The raw materials for preparing the urethane ester A include diisocyanate A and a monohydric alcohol. The monohydric alcohol has the structure R2-OH, and the diisocyanate A has the structure OCN-R1-NCO. R1 and R2 in Formula I have the same range of values.

3. The polyisocyanate composition according to claim 2, characterized in that, The monohydric alcohols include monohydric alcohols with 2 to 10 carbon atoms.

4. The polyisocyanate composition according to claim 3, characterized in that, The monohydric alcohol is an aliphatic monohydric alcohol with 2 to 10 carbon atoms.

5. The polyisocyanate composition according to claim 4, characterized in that, The aliphatic monohydric alcohol includes any one or a combination of at least two of methanol, ethanol, propanol, n-butanol, hexanol, isobutanol, or 2-ethylhexanol.

6. The polyisocyanate composition according to claim 1, characterized in that, The raw materials for preparing the urea-formate B include diisocyanate B and diol. The structure of the diol is HO-R3-OH, and the structure of the diisocyanate B is OCN-R4-NCO. R3 and R4 have the same range of values ​​as R3 and R4 in Formula ⅠI.

7. The polyisocyanate composition according to claim 6, characterized in that, The diols include diols with 2 to 12 carbon atoms.

8. The polyisocyanate composition according to claim 7, characterized in that, The diol is an aliphatic diol with 2 to 12 carbon atoms.

9. The polyisocyanate composition according to claim 8, characterized in that, The aliphatic diols include any one or a combination of at least two of the following: ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethyl-hexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, or 2,2-diethyl-1,3-propanediol.

10. The polyisocyanate composition according to claim 2, characterized in that, The diisocyanate A independently comprises any one or a combination of at least two of the following: tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or lysine diisocyanate.

11. The polyisocyanate composition according to claim 6, characterized in that, The diisocyanate B independently comprises any one or a combination of at least two of the following: tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, or lysine diisocyanate.

12. The polyisocyanate composition according to claim 10, characterized in that, The diisocyanate A is independently pentamethylene diisocyanate and / or hexamethylene diisocyanate.

13. The polyisocyanate composition according to claim 11, characterized in that, The diisocyanate B is independently pentamethylene diisocyanate and / or hexamethylene diisocyanate.

14. The polyisocyanate composition according to any one of claims 1-13, characterized in that, The urea carbamate is prepared by method A or method B; Method A includes: reacting diisocyanate and monohydric alcohol, then adding dihydric alcohol to react again, to obtain the urea carbamate composition; Method B includes the following steps: (B1) Reaction of diisocyanate A and monohydric alcohol yields urethane A; reaction of diisocyanate B and dihydric alcohol yields urethane B. (B2) Mix urethane A and urethane B obtained in step (B1) to obtain the urethane composition.

15. The polyisocyanate composition according to claim 14, characterized in that, In method A, the mass of the monohydric alcohol is 0.05 to 5% based on the mass of the diisocyanate being 100%.

16. The polyisocyanate composition according to claim 14, characterized in that, In method A, the reaction time for the diisocyanate and the monohydric alcohol is 2 to 5 hours.

17. The polyisocyanate composition according to claim 14, characterized in that, In method A, the reaction temperature for the reaction of the diisocyanate and the monohydric alcohol is 90~120℃.

18. The polyisocyanate composition according to claim 14, characterized in that, In method A, the mass of the diol is 0.01 to 5% based on the mass of the diisocyanate being 100%.

19. The polyisocyanate composition according to claim 14, characterized in that, In method A, the reaction temperature for adding diol to carry out the reaction is 50~80℃.

20. The polyisocyanate composition according to claim 14, characterized in that, In method A, the reaction with the addition of diols ends when the conversion rate of diisocyanate is 30-60%.

21. The polyisocyanate composition according to claim 14, characterized in that, In method B, the reaction temperature for reacting the diisocyanate and the monohydric alcohol is 80~120℃.

22. The polyisocyanate composition according to claim 14, characterized in that, In method B, the reaction time for reacting the diisocyanate and the monohydric alcohol is 0.5 to 2 h.

23. The polyisocyanate composition according to claim 14, characterized in that, In method B, the reaction temperature for reacting the diisocyanate and the diol is 80~120℃.

24. The polyisocyanate composition according to claim 14, characterized in that, In method B, the reaction time for reacting the diisocyanate and the diol is 0.5 to 2 h.

25. The polyisocyanate composition according to claim 14, characterized in that, In method B, the reaction of diisocyanate and monohydric alcohol and the reaction of diisocyanate and dihydric alcohol are both carried out under the catalytic conditions of a urea-formylation catalyst.

26. The polyisocyanate composition according to claim 25, characterized in that, The ureocarboxylation catalyst includes bismuth 2-ethylhexanoate.

27. The polyisocyanate composition according to claim 1, characterized in that, The isocyanate polymer includes isocyanate trimer.

28. A method for preparing the polyisocyanate composition according to any one of claims 1-27, characterized in that, The preparation method includes method C or method D; Method C includes: mixing the urea carbamate composition as described in claim 1 with the isocyanate polymer to obtain the polyisocyanate composition; Method D includes the following steps: (D1) The diisocyanate and monohydric alcohol are reacted to obtain a reaction solution containing urethane A; (D2) The reaction solution containing urethane A obtained in step (D1), the diol and the catalyst are reacted, and a terminator is added to obtain the polyisocyanate composition.

29. The preparation method according to claim 28, characterized in that, The mass of the catalyst in step (D2) is 10~1000 ppm, based on the mass of the diisocyanate in step (D1) being 100%.

30. The preparation method according to claim 28, characterized in that, The catalyst includes any one or at least two combinations of quaternary ammonium catalysts, silazane catalysts, alkylphosphine catalysts, tertiary amine catalysts, or manniene base catalysts.

31. The preparation method according to claim 30, characterized in that, The quaternary ammonium catalysts include quaternary ammonium base catalysts and / or quaternary ammonium salt catalysts.

32. The preparation method according to claim 31, characterized in that, The quaternary ammonium catalyst is any one or at least a combination of two of the following: choline hydroxide, trimethylhydroxyethylammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, hexamethylbisammonium hydroxide, tetramethylammonium, tetraethylammonium formate, tetraethylammonium acetate, tetraethylammonium decanoate, trimethylhydroxypropylammonium formate, trimethylhydroxypropylammonium acetate, trimethylhydroxypropyl octanoate, trimethylhydroxypropylammonium decanoate, trimethylhydroxyethylammonium formate, trimethylhydroxyethylammonium acetate, or trimethylhydroxyethylammonium decanoate.

33. The preparation method according to claim 32, characterized in that, The quaternary ammonium catalyst is tetraethylammonium hydroxide and / or trimethylhydroxypropyl octanoate ammonium.

34. The preparation method according to claim 30, characterized in that, The silazane catalysts include hexamethyldisilazane and / or heptamethyldisilazane.

35. The preparation method according to claim 30, characterized in that, The alkylphosphine catalysts include tributylphosphine and / or triphenylphosphine.

36. The preparation method according to claim 30, characterized in that, The tertiary amine catalyst includes triethylamine.

37. The preparation method according to claim 28, characterized in that, The terminating agent includes an acidic substance.

38. The preparation method according to claim 37, characterized in that, The terminating agent is any one or a combination of at least two of phosphoric acid, formic acid, benzoic acid, benzoyl chloride, or diisooctyl phosphate.

39. The preparation method according to claim 28, characterized in that, The addition of the terminator further includes a step of removing unreacted diisocyanate.

40. The preparation method according to claim 39, characterized in that, The method for removing unreacted diisocyanates includes any one or a combination of at least two of the following: thin-film evaporation, falling-film evaporation, short-path evaporation, or vacuum distillation.

41. A coating composition, characterized in that, The coating composition comprises the polyisocyanate composition and polymeric polyol as described in any one of claims 1-27; The number average molecular weight of the polymer polyol is 2000~8000.

42. The coating composition according to claim 41, characterized in that, The molar ratio of isocyanate groups in the polyisocyanate composition to hydroxyl groups in the polymer polyol is (1~1.5):

1.

43. The coating composition according to claim 41, characterized in that, The polymer polyols include acrylic polyols and / or polyester polyols.

44. The coating composition according to claim 43, characterized in that, The raw materials for preparing the acrylic polyols include any one or a combination of at least two of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, or 2-hydroxybutyl acrylate.

45. The coating composition according to claim 43, characterized in that, The raw materials for preparing the polyester polyol include acid monomers and alcohol monomers.

46. ​​The coating composition according to claim 45, characterized in that, The acid monomers include any one or a combination of at least two of succinic acid, adipic acid, sebacic acid, or maleic anhydride.

47. The coating composition according to claim 45, characterized in that, The alcohol monomers include any one or a combination of at least two of ethylene glycol, propylene glycol, diethylene glycol, or neopentyl glycol.

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