Hybrid of inorganic material and alkyd resin as well as in-situ polymerization preparation method and application of hybrid

Abstract

The invention belongs to the technical field of resin, and discloses a hybrid of an inorganic material and alkyd resin as well as an in-situ polymerization preparation method and application of the hybrid. The in-situ polymerization preparation method comprises the following steps: mixing nano titanium dioxide, oleic acid, polyol, anhydride and hypophosphorous acid, heating to reflux and reacting in a protective gas atmosphere, then continuously heating, and finally cooling to prepare a hybrid of an inorganic material and alkyd resin. The hybrid of the inorganic material and the alkyd resin prepared by the preparation method disclosed by the invention is applied to a polyurethane coating, the hard drying time is short, the construction efficiency is high, and the hardness of a formed coating is high, for example, the pencil hardness is not less than 3H.

Description

Technical Field

[0001] The invention belongs to the technical field of resins, and particularly relates to a hybrid of an inorganic material and an alkyd resin and an in-situ polymerization preparation method and application thereof. Background Art

[0002] Alkyd resins are widely used in polyurethane coatings. However, when existing alkyd resins are used in polyurethane coatings, the mechanical strength of the coatings formed is often insufficient. For example, the hardness of the coatings is difficult to exceed 2H.

[0003] Chinese patent application number 201711317194.8 discloses a method for preparing an in-situ polymerization-modified unsaturated polyester resin, which comprises reacting hydroxy-modified carbon nanotubes, maleic anhydride, dimer acid, phthalic anhydride, a catalyst and 1,2-propylene glycol, and reacting the product with an initiator and a promoter to form a product.

[0004] Chinese patent application number 202410048778.3 discloses an organic-inorganic hybrid multifunctional anti-fog coating, a preparation method and a coating thereof. The preparation method comprises the following steps: mixing tetraethyl orthosilicate, a vinyl silane coupling agent, alcohol, water and an acid, and sequentially performing hydrolysis and static aging to obtain a vinyl silica sol; mixing a fluorine-containing acrylate monomer, an amino-containing acrylate monomer, a benzene solvent and an initiator for polymerization reaction to obtain a copolymer; mixing the copolymer, a brominated alkane and acetonitrile for protonation reaction to obtain an amphiphilic polymer; mixing the vinyl silica sol, an amphiphilic polymer, water and a photoinitiator to obtain an organic-inorganic hybrid multifunctional anti-fog coating.

[0005] The Chinese patent application number 202311692936.0 discloses a resin composition, a UV light-cured organic-inorganic hybrid coating and a preparation method thereof. The resin composition includes the following raw material components by mass: 25-60 parts of UV light-cured oligomer, 30-70 parts of inorganic resin, 5-25 parts of active diluent, 2-5 parts of photoinitiator, 0.5-2 parts of leveling agent, and 50-150 parts of divalent acid ester. The prepared organic-inorganic hybrid coating has ultra-high heat resistance, permeability and excellent hardness.

[0006] The coatings formed by the above prior art often have insufficient mechanical strength, some coatings take too long to dry, and the construction efficiency is low. It is particularly important to point out that although there are some alkyd resins modified by inorganic substances in the prior art, they cannot be applied to two-component polyurethane coatings.

[0007] Therefore, there is an urgent need to provide a new resin that can be applied to coatings so that the formed coating has high hardness and a short drying time. Summary of the invention

[0008] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a hybrid of an inorganic material and an alkyd resin and an in-situ polymerization preparation method and application thereof. The hybrid of an inorganic material and an alkyd resin prepared by the preparation method of the present invention is applied to a polyurethane (PU) coating, has a short actual drying time, high construction efficiency, and a high hardness of the formed coating, for example, a pencil hardness of not less than 3H.

[0009] A first aspect of the present invention provides a method for preparing a hybrid of an inorganic material and an alkyd resin by in-situ polymerization.

[0010] Specifically, a method for preparing a hybrid of an inorganic material and an alkyd resin by in-situ polymerization comprises the following steps:

[0011] Nano titanium dioxide, oleic acid, polyol, acid anhydride and hypophosphorous acid are mixed, heated to reflux in a protective gas atmosphere, reacted, then heated further, and finally cooled to obtain a hybrid of the inorganic material and alkyd resin.

[0012] Preferably, the polyol includes pentaerythritol, neopentyl glycol and diethylene glycol.

[0013] Preferably, the acid anhydride includes maleic anhydride and phthalic anhydride.

[0014] Preferably, the protective gas includes nitrogen or a rare gas, such as argon or helium.

[0015] Preferably, the weight ratio of the nano-titanium dioxide, oleic acid, polyol, acid anhydride and hypophosphorous acid is 0.1-15:(15-25):(15-25):(20-30):(0.10-0.50).

[0016] Preferably, the weight ratio of the nano titanium dioxide, oleic acid, polyol, acid anhydride and hypophosphorous acid is 0.1-9.65: (20.38-21.78): (21.94-23.45): (23.51-25.13): (0.10-0.20).

[0017] Preferably, the reaction temperature is 150-158° C., and the reaction time is 2-4 hours. More preferably, the reaction temperature is 152-156° C., and the reaction time is 3-4 hours.

[0018] Preferably, the temperature is continued to be raised to 210-215° C., and the esterification is performed until the acid value does not exceed 10 mgKOH / g. At this time, the viscosity of the obtained product is acceptable.

[0019] Preferably, during the mixing process, xylene and / or 2,6-di-tert-butyl-4-methylphenol are also added.

[0020] Preferably, after cooling, n-butyl acetate is also added.

[0021] Preferably, the temperature is lowered to below 180° C. When the temperature drops below this level, n-butyl acetate may be added to adjust the solid content of the product.

[0022] Preferably, in the preparation method, 1.54-2.5 parts of xylene, 0.08-0.25 parts of 2,6-di-tert-butyl-4-methylphenol, and 21.57-27.64 parts of n-butyl acetate are further added by weight.

[0023] Preferably, in the preparation method, the added amount of each raw material component is, by weight, 0.1-9.65 parts of nano titanium dioxide, 20.38-21.78 parts of oleic acid, 21.94-23.45 parts of polyol, 23.51-25.13 parts of acid anhydride, 0.10-0.20 parts of hypophosphorous acid, 1.54-2.5 parts of xylene, 0.08-0.25 parts of 2,6-di-tert-butyl-4-methylphenol, and 21.57-27.64 parts of n-butyl acetate.

[0024] Preferably, the polyol comprises, by weight, 12.91-13.80 parts of pentaerythritol, 4.29-4.59 parts of neopentyl glycol, and 4.74-5.06 parts of diethylene glycol.

[0025] The second aspect of the present invention provides a method for preparing a hybrid of an inorganic material and an alkyd resin by in-situ polymerization.

[0026] Specifically, a hybrid of an inorganic material and an alkyd resin is prepared by the above in-situ polymerization preparation method.

[0027] Preferably, the hybrid of the inorganic material and the alkyd resin has a viscosity of 9000-17000 mPa·S at 25° C. and an acid value of 10-11 mgKOH / g.

[0028] Preferably, the hybrid of the inorganic material and the alkyd resin has a solid content of 69.47-74.9% and a hydroxyl value of 122-131 KOH / g.

[0029] Preferably, the hybrid of the inorganic material and the alkyd resin is a yellow viscous transparent liquid.

[0030] The third aspect of the present invention provides an application of a hybrid of an inorganic material and an alkyd resin.

[0031] A coating comprises a hybrid of an inorganic material and an alkyd resin prepared by the in-situ polymerization preparation method.

[0032] Preferably, the coating comprises a polyurethane coating; further preferably, the coating is a two-component polyurethane coating.

[0033] Preferably, the polyurethane coating comprises component A and a curing agent containing a diluent, and the weight ratio of component A to the curing agent containing a diluent is 1:(0.5-1).

[0034] Preferably, the component A also includes auxiliary agents, and the auxiliary agents include leveling agents and defoaming agents.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] (1) The hybrid of the inorganic material and the alkyd resin of the present invention uses nano titanium dioxide to modify the alkyd resin to obtain the hybrid of the nano titanium dioxide and the alkyd resin. The present invention utilizes the surface polyhydroxyl characteristics of the nano titanium dioxide to introduce the oleic acid modified alkyd resin, directly adds the nano titanium dioxide to the oleic acid modified alkyd resin formula system, and dehydrates by xylene reflux, esterification and polycondensation. The present invention adopts an in-situ polymerization preparation process to obtain a hybrid of an inorganic material and an alkyd resin.

[0037] (2) The hybrid of an inorganic material and an alkyd resin of the present invention solves the problem that nano-modified alkyd resin can only be applied to a single-component system, and is applied to a two-component polyurethane coating (or a two-component alkyd polyurethane wood paint system) with excellent performance. The pencil hardness of the coating film can reach 3H or above, the actual drying time is short, and the construction efficiency is high. DETAILED DESCRIPTION

[0038] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0039] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0040] The nano titanium dioxide used below is LS-100 photocatalyst produced by Liaoning University Blue Water Manufacturing Co., Ltd. Its composition is: TiO2 mass concentration is 1%, particle size: 0.38-0.96nm. Components: nano titanium dioxide, supramolecular nanocluster self-assembly aid, deionized water.

[0041] Example 1

[0042] An in-situ polymerization preparation method of a hybrid of an inorganic material and an alkyd resin comprises the following steps:

[0043] Weigh the following parts by weight of raw materials:

[0044] 1.05 parts of a commercially available 1% nano titanium dioxide solution, 21.78 parts of oleic acid, 13.80 parts of pentaerythritol, 4.59 parts of neopentyl glycol, 5.06 parts of diethylene glycol, 0.53 parts of maleic anhydride, 24.60 parts of phthalic anhydride, 0.16 parts of hypophosphorous acid, 2.04 parts of xylene, 26.31 parts of n-butyl acetate, and 0.08 parts of 2,6-di-tert-butyl-4-methylphenol;

[0045] In a reaction kettle equipped with a fractionating column, a condenser and a water separator, other components except n-butyl acetate are added, nitrogen is introduced, and the temperature is raised to reflux at about 156° C. After reflux, the reaction is carried out for 4 hours, and then the temperature is slowly raised to 215° C., and when the acid value is esterified to 10 mgKOH / g, the temperature is lowered to below 180° C., and n-butyl acetate is added to obtain a hybrid of an inorganic material and an alkyd resin (also called a hybrid of an inorganic material and an alkyd resin modified with 33 oil oleic acid).

[0046] The hybrid of the inorganic material and the alkyd resin has a viscosity of 9000 mPa·S / 25° C., an acid value of 10 mgKOH / g, a solid content of 70.25%, and a hydroxyl value of 131 mgKOH / g.

[0047] Example 2

[0048] An in-situ polymerization preparation method of a hybrid of an inorganic material and an alkyd resin comprises the following steps:

[0049] Weigh the following parts by weight of raw materials:

[0050] 4.85 parts of commercially available nano titanium dioxide solution with a mass concentration of 1%, 21.12 parts of oleic acid, 13.38 parts of pentaerythritol, 4.45 parts of neopentyl glycol, 4.91 parts of diethylene glycol, 0.51 parts of maleic anhydride, 23.85 parts of phthalic anhydride, 0.10 parts of hypophosphorous acid, 1.54 parts of xylene, 25.14 parts of n-butyl acetate, and 0.15 parts of 2,6-di-tert-butyl-4-methylphenol;

[0051] In a reaction kettle equipped with a fractionating column, a condenser and a water separator, other components except n-butyl acetate are added, nitrogen is introduced, and the temperature is raised to reflux at about 156° C. After reflux, the reaction is carried out for 4 hours, and then the temperature is slowly raised to 215° C., and when the acid value is esterified to 12 mgKOH / g, the temperature is lowered to below 180° C., and n-butyl acetate is added to obtain a hybrid of an inorganic material and an alkyd resin (also called a hybrid of an inorganic material and an alkyd resin modified with 31 oil oleic acid).

[0052] The hybrid of the inorganic material and the alkyd resin has a viscosity of 12000 mPa·S / 25° C., an acid value of 12 mgKOH / g, a solid content of 72.1%, and a hydroxyl value of 127 mgKOH / g.

[0053] Example 3

[0054] An in-situ polymerization preparation method of a hybrid of an inorganic material and an alkyd resin comprises the following steps:

[0055] Weigh the following parts by weight of raw materials:

[0056] 2.35 parts of a commercially available nano titanium dioxide solution with a mass concentration of 1%, 21.12 parts of oleic acid, 13.38 parts of pentaerythritol, 4.45 parts of neopentyl glycol, 4.91 parts of diethylene glycol, 0.51 parts of maleic anhydride, 23.85 parts of phthalic anhydride, 0.10 parts of hypophosphorous acid, 1.54 parts of xylene, 27.64 parts of n-butyl acetate, and 0.15 parts of 2,6-di-tert-butyl-4-methylphenol;

[0057] In a reaction kettle equipped with a fractionating column, a condenser and a water separator, other components except n-butyl acetate are added, nitrogen is passed through, and the temperature is raised to reflux at about 154° C. After reflux, the reaction is carried out for 4 hours, and then the temperature is slowly raised to 215° C., and when the acid value is esterified to 11 mgKOH / g, the temperature is lowered to below 180° C., and n-butyl acetate is added to obtain a hybrid of an inorganic material and an alkyd resin (also called a hybrid of an inorganic material and an alkyd resin modified with 33 oil oleic acid).

[0058] The hybrid of the inorganic material and the alkyd resin has a viscosity of 10000 mPa·S / 25° C., an acid value of 11 mgKOH / g, a solid content of 69.5%, and a hydroxyl value of 129 mgKOH / g.

[0059] Example 4

[0060] An in-situ polymerization preparation method of a hybrid of an inorganic material and an alkyd resin comprises the following steps:

[0061] Weigh the following parts by weight of raw materials:

[0062] 9.65 parts of a commercially available nano titanium dioxide solution with a mass concentration of 1%, 20.38 parts of oleic acid, 12.91 parts of pentaerythritol, 4.29 parts of neopentyl glycol, 4.74 parts of diethylene glycol, 0.49 parts of maleic anhydride, 23.02 parts of phthalic anhydride, 0.20 parts of hypophosphorous acid, 2.50 parts of xylene, 21.57 parts of n-butyl acetate, and 0.25 parts of 2,6-di-tert-butyl-4-methylphenol;

[0063] In a reaction kettle equipped with a fractionating column, a condenser and a water separator, other components except n-butyl acetate are added, nitrogen is introduced, and the temperature is raised to reflux at about 156° C. After reflux, the reaction is carried out for 4 hours, and then the temperature is slowly raised to 215° C., and when the acid value is esterified to 8 mgKOH / g, the temperature is lowered to below 180° C., and n-butyl acetate is added to obtain a hybrid of an inorganic material and an alkyd resin (also called a hybrid of an inorganic material and an alkyd resin modified with 29-oil oleic acid).

[0064] The hybrid of the inorganic material and the alkyd resin has a viscosity of 17000 mPa·S / 25° C., an acid value of 8 mgKOH / g, a solid content of 74.9%, and a hydroxyl value of 122 mgKOH / g.

[0065] Comparative Example 1

[0066] Compared with Example 1, the difference of Comparative Example 1 is that the commercially available nano titanium dioxide solution with a mass concentration of 1% is not added, and the other compositions and processes are the same as those of Example 1.

[0067] Comparative Example 2

[0068] Compared with Example 2, the only difference of Comparative Example 2 is that the commercially available nano titanium dioxide solution with a mass concentration of 1% is not added, and the other compositions and processes are the same as those of Example 2.

[0069] Comparative Example 3

[0070] Compared with Example 3, the only difference of Comparative Example 3 is that the commercially available nano titanium dioxide solution with a mass concentration of 1% is not added, and the other compositions and processes are the same as those of Example 3.

[0071] Comparative Example 4

[0072] Compared with Example 4, the only difference of Comparative Example 4 is that the commercially available nano titanium dioxide solution with a mass concentration of 1% is not added, and the other compositions and processes are the same as those of Example 4.

[0073] Comparative Example 5

[0074] Comparative Example 5 is an alkyd resin modified with nano-titanium dioxide prepared in Example 1 of CN112759748 A.

[0075] Product effect testing

[0076] The performance parameters of the products prepared in Examples 1-4 and Comparative Examples 1-5 (the products in the examples are hybrids of inorganic materials and alkyd resins, while the products in the comparative examples do not contain inorganic materials) are shown in Table 1.

[0077] Table 1

[0078]

[0079]

[0080] The products prepared in the above examples and comparative examples are used to prepare polyurethane coatings (also called two-component polyurethane glossy paints).

[0081] The polyurethane coating comprises component A, a curing agent containing a diluent and a diluent, and the weight ratio of component A, the curing agent containing a diluent and the diluent is 1:1:0.3.

[0082] The composition of component A is shown in Table 2 (the numerical units in Table 2 are parts by weight).

[0083] Table 2

[0084]

[0085]

[0086] “-” in the table means no addition.

[0087] The leveling agent in the table is Huaxia Additive HX-3130, and the defoaming agent is Huaxia Additive HX-2500.

[0088] The preparation process of component A is as follows: the product prepared in the embodiment or comparative example is mixed with propylene glycol methyl ether acetate, part of n-butyl acetate and xylene, the mixing stirring speed is 300 rpm, stirring for 10 minutes, then adding the leveling agent and the defoaming agent, stirring at a speed of 1600 rpm for 15 minutes, and then adding the remaining 5 parts of n-butyl acetate, 500 rpm, stirring for 10 minutes, to obtain component A.

[0089] The preparation process of the curing agent containing a diluent is as follows: the commercially available Shandong Yantai Wanhua L-75 curing agent is diluted with n-butyl acetate at a weight ratio of 40:60 to form a curing agent with a solid content of 30%.

[0090] The preparation process of the diluent is as follows: 50 parts by weight of n-butyl acetate and 50 parts by weight of xylene are mixed to prepare the diluent.

[0091] The polyurethane coating including component A, curing agent containing diluent and diluent were mixed and stirred evenly, and after standing for 10 minutes, the polyurethane coating was sprayed on a 30cm*20cm sticker board using an air spray gun. The spraying was completed (the spraying amount was 0.02g / cm 2), refer to the national standard GB / T 23997-2009 "Solvent-based polyurethane wood coatings for interior decoration and renovation", and test it after it is dried at room temperature for 48 hours. The actual drying time test is carried out according to the provisions of GB / T 1728-1979 Method A, the pencil hardness is carried out according to the provisions of GB / T6739-2006, and the gloss is carried out according to the provisions of GB / T 9754-2007. The results are shown in Table 3.

[0092] Table 3

[0093]

[0094] It can be seen from Table 3 that the actual drying time of the polyurethane coating formed by the product prepared in the example is shorter than that of the comparative example, and the hardness of the polyurethane coating formed by the product prepared in the example is significantly higher than that of the comparative example.

Claims

1. A method for preparing a hybrid of an inorganic material and an alkyd resin by in-situ polymerization, characterized in that: The following steps are involved: Nano titanium dioxide, oleic acid, polyol, acid anhydride and hypophosphorous acid are mixed, heated to reflux in a protective gas atmosphere, reacted, then heated further, and finally cooled to obtain a hybrid of the inorganic material and alkyd resin.

2. The in-situ polymerization preparation method according to claim 1, characterized in that: The polyol includes pentaerythritol, neopentyl glycol and diethylene glycol; and / or, the acid anhydride includes maleic anhydride and phthalic anhydride.

3. The in-situ polymerization preparation method according to claim 1, characterized in that: The weight ratio of the nano titanium dioxide, oleic acid, polyol, acid anhydride and hypophosphorous acid is 0.1-15:(15-25):(15-25):(20-30):(0.10-0.50).

4. The in-situ polymerization preparation method according to claim 1, characterized in that: The reaction temperature is 150-158° C., and the reaction time is 2-4 hours; and / or, the continued heating is to heat to 210-215° C., and esterification is performed until the acid value does not exceed 10 mgKOH / g.

5. The in-situ polymerization preparation method according to claim 1, characterized in that: During the mixing process, xylene and / or 2,6-di-tert-butyl-4-methylphenol are added; and / or after the cooling, n-butyl acetate is added.

6. The in-situ polymerization preparation method according to claim 5, characterized in that: In the preparation method, 1.54-2.5 parts of xylene, 0.08-0.25 parts of 2,6-di-tert-butyl-4-methylphenol, and 21.57-27.64 parts of n-butyl acetate are further added by weight.

7. The in-situ polymerization preparation method according to claim 6, characterized in that: In the preparation method, the added amount of each raw material component is, by weight, 0.1-9.65 parts of nano titanium dioxide, 20.38-21.78 parts of oleic acid, 21.94-23.4 parts of polyol, 23.51-25.13 parts of anhydride, 0.10-0.20 parts of hypophosphorous acid, 1.54-2.5 parts of xylene, 0.08-0.25 parts of 2,6-di-tert-butyl-4-methylphenol, and 21.57-27.64 parts of n-butyl acetate.

8. A hybrid of an inorganic material and an alkyd resin, characterized in that: The hybrid of the inorganic material and the alkyd resin is prepared by the in-situ polymerization preparation method according to any one of claims 1 to 7; and the viscosity of the hybrid of the inorganic material and the alkyd resin at 25° C. is 9000-17000 mPa·S, and the acid value is 10-11 mgKOH / g.

9. A coating, characterized in that: The invention comprises a hybrid of an inorganic material and an alkyd resin prepared by the in-situ polymerization preparation method according to any one of claims 1 to 7.

10. The coating according to claim 9, characterized in that The coating is a two-component polyurethane coating.

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