A method for preparing polyhedral oligomeric silsesquioxane containing propylene metallocene

Abstract

The present invention relates to the technical field of silsesquioxane preparation, and in particular to a method for preparing a polyhedral oligomeric silsesquioxane containing acryl metallocene. Specifically, trisilanol heptaisobutyl polysilsesquioxane is dissolved in a solvent, (methacryloyloxymethyl) methyldimethoxysilane is added, and the mixture is stirred and reacted in a water bath under an inert atmosphere, and an isopropanol solution of chloroplatinic acid, vinyl ferrocene, and dimethylallyl triammonium lanthanum diphosphate are continuously added, and the mixture is stirred and heated to react, and then the solvent is removed by reduced pressure distillation, and alcohol is added for repeated washing, and the polyhedral oligomeric silsesquioxane containing acryl metallocene is obtained after drying. The polyhedral oligomeric silsesquioxane containing acryl metallocene prepared by the method has excellent thermal stability, chemical corrosion resistance, and mechanical strength.

Description

Technical Field

[0001] The invention relates to the technical field of silsesquioxane preparation, in particular to a method for preparing polyhedral oligomeric silsesquioxane containing acryl metallocene. Background Art

[0002] Cage-type polyhedral oligomeric silsesquioxane (POSS) is a new type of organic-inorganic hybrid material. Its special nanostructure, nanosize effect, cross-linking effect and effective modification of polymers have attracted great attention.

[0003] The methods for monofunctionalization of POSS include silane hydrolysis method, vertex-capping method and functional group derivatization method. Among them, the vertex-capping method is a commonly used synthesis method due to its simple and efficient synthesis and short preparation cycle.

[0004] Chinese patent publication number CN107325123B discloses a polyhedral oligomeric silsesquioxane containing multiple alkenyl or alkynyl groups, which is a cage-type polyhedral oligomeric silsesquioxane containing dienyl or alkynyl groups, a double tower type polyhedral oligomeric silsesquioxane containing dienyl or alkynyl groups, and a double tower type polyhedral oligomeric silsesquioxane containing tetraenyl or tetraalkynyl groups. The polyhedral oligomeric silsesquioxane containing multiple alkenyl or alkynyl groups is synthesized as follows: first, a polyhedral oligomeric silsesquioxane containing terminal alkenyl groups is subjected to a thiol addition reaction with an alkyl carboxylic acid containing a thiol group, and then a condensation reaction is carried out with an alkenylamine or an alkynylamine to obtain a polyhedral oligomeric silsesquioxane containing multiple alkenyl or alkynyl groups. Wherein, the polyhedral oligomeric silsesquioxane contains multiple unsaturated bonds, which can be further polymerized with a monomer or condensed with a difunctionalized substance, so that the polyhedral oligomeric silsesquioxane is connected to the polymer backbone.

[0005] Chinese patent publication number CN110343253B discloses a monocarboxylic acid type polyhedral oligomeric silsesquioxane containing a lanthanide metal, a preparation method thereof, and a composition containing the same, wherein the monocarboxylic acid type polyhedral oligomeric silsesquioxane containing a lanthanide metal is obtained by reacting a polyhedral oligomeric silsesquioxane containing a monocarboxyl group, a lanthanide metal chloride, and a sodium alcoholate as raw materials; the POSS structure in the monocarboxylic acid type polyhedral oligomeric silsesquioxane containing a lanthanide metal of the present invention is not destroyed, and the POSS structure is a T8 type condensation structure, and the POSS structure can significantly reduce the curing temperature of materials such as cyanate resins and benzoxazine resins, and has a significant curing catalytic effect.

[0006] There are no special requirements for the structure or type of peripheral organic functional groups of POSS, and its synthesis route is relatively simple, so POSS is used as a conventional nanofiller. However, this method has problems such as nanoparticle agglomeration and poor component compatibility. To this end, researchers doped POSS by chemical bonding to solve its compatibility problem, which adds complexity to the synthesis of POSS monomers, and has some disadvantages such as narrow selection of synthetic monomers, lengthy synthesis cycle, difficult purification and low yield, and there are few reports on its application. Summary of the invention

[0007] In order to solve the shortcomings and deficiencies of the prior art, the primary object of the present invention is to provide a method for preparing polyhedral oligomeric silsesquioxane containing propylene metallocene.

[0008] Another object of the present invention is to provide polyhedral oligomeric silsesquioxane containing acryl metallocene obtained by the above preparation method.

[0009] The purpose of the present invention is achieved through the following technical solutions:

[0010] A method for preparing polyhedral oligomeric silsesquioxane containing propylene metallocene, characterized in that it comprises the following steps:

[0011] S1: In a reaction kettle, weigh 8-16 parts of trisilanol heptaisobutyl polysilsesquioxane, 100-160 parts of solvent, and 3-7 parts of (methacryloyloxymethyl)methyldimethoxysilane, introduce nitrogen, and stir in a water bath to react;

[0012] S2: Continue to add 0.1-0.7 parts of isopropanol solution of chloroplatinic acid, and then add 0.03-0.5 parts of vinylferrocene and 0.01-0.1 parts of dimethylallyl triammonium lanthanum diphosphate, stirring and heating to react for 20-50 minutes, and then remove the solvent by distillation under reduced pressure;

[0013] S3: adding alcohol to wash repeatedly, and then drying in a vacuum oven to obtain polyhedral oligomeric silsesquioxane containing propenyl metallocene.

[0014] In some embodiments of the present invention, the solvent is selected from at least one of dichloromethane, dichloroethane, dichloropropane, methyl acetate, dimethyl carbonate or propylene glycol methyl ether acetate.

[0015] In some embodiments of the present invention, the water bath temperature in step S1 is 16-28°C.

[0016] In some embodiments of the present invention, the stirring speed in step S1 is 185-445 rpm, and the stirring reaction time is 12-24 h.

[0017] In some embodiments of the present invention, the vacuum degree of the vacuum oven in step S1 is not higher than 500 Pa, and the oven temperature is 40-60°C.

[0018] In some embodiments of the present invention, the reaction temperature of step S2 is 50-60°C

[0019] In some embodiments of the present invention, the mass percentage of the isopropanol solution of chloroplatinic acid in step S2 is 5-10%.

[0020] In some embodiments of the present invention, the alcohol in step S3 is selected from at least one of methanol, ethanol or propanol.

[0021] In some embodiments of the present invention, the vacuum degree of the vacuum oven in step S3 is not higher than 600 Pa, and the oven temperature is 50-75°C.

[0022] The reaction mechanism is:

[0023] (1) the hydroxyl group of trisilanol heptaisobutyl polysilsesquioxane undergoes a condensation reaction with the dimethoxysilane of (methacryloyloxymethyl)methyldimethoxysilane to obtain acryl-containing polysilsesquioxane;

[0024] (2) The silane-hydrogen bonds of the acryl-containing polysilsesquioxane continue to undergo a silylation reaction with vinyl ferrocene and dimethylallyl triammonium lanthanum diphosphate, thereby introducing a trace amount of metallocene and organic lanthanum into the framework of the polysilsesquioxane to obtain a polyhedral oligomeric silsesquioxane containing acryl metallocene.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. Thermal stability: The introduction of metallocene and organic lanthanum can effectively hinder the degradation and decomposition of polymer chains and effectively improve the thermal stability of polysilsesquioxane.

[0027] 2. Chemical corrosion resistance: After the introduction of metallocene or organic lanthanum into polysilsesquioxane, a denser molecular structure can be formed, thereby reducing the possibility of chemical penetration and corrosion.

[0028] 3. Mechanical properties: The introduction of metallocene and organic lanthanum can produce strong interactions with siloxane groups to form a stronger molecular structure, thereby improving the mechanical strength of the polymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is a scanning electron microscope photo of propylene metallocene polyhedral oligomeric silsesquioxane. DETAILED DESCRIPTION

[0030] The present invention is described in detail below through specific implementation modes. Through these descriptions, the characteristics and advantages of the present invention will become clearer and more specific.

[0031] Figure 1 SEM photo of propylene metallocene polyhedral oligomeric silsesquioxane

[0032] Example 1

[0033] A method for preparing polyhedral oligomeric silsesquioxane containing propylene metallocene, characterized in that it comprises the following steps:

[0034] S1: In a reaction kettle, weigh 8 g of trisilanol heptaisobutyl polysilsesquioxane, 100 g of solvent, and 3 g of (methacryloyloxymethyl)methyldimethoxysilane, introduce nitrogen, and stir in a water bath to react;

[0035] S2: Continue to add 0.1g of isopropanol solution of chloroplatinic acid, then add 0.03g of vinylferrocene and 0.01g of lanthanum triammonium dimethylallyl diphosphate, stir and heat to react for 20 minutes, and then remove the solvent by distillation under reduced pressure;

[0036] S3: adding alcohol to wash repeatedly, and then drying in a vacuum oven to obtain polyhedral oligomeric silsesquioxane containing propenyl metallocene.

[0037] The solvent selected is dichloromethane.

[0038] The water bath temperature in step S1 is 16°C.

[0039] The stirring speed of step S1 is 185 rpm, and the stirring reaction time is 12 h.

[0040] The vacuum degree of the vacuum oven in step S1 is not higher than 500 Pa, and the oven temperature is 40°C.

[0041] The reaction temperature of step S2 is 50°C

[0042] The mass percentage of the isopropanol solution of chloroplatinic acid in step S2 is 5%.

[0043] The alcohol in step S3 is selected from methanol.

[0044] The vacuum degree of the vacuum oven in step S3 is not higher than 600 Pa, and the oven temperature is 50°C.

[0045] Example 2

[0046] A method for preparing polyhedral oligomeric silsesquioxane containing propylene metallocene, characterized in that it comprises the following steps:

[0047] S1: In a reaction kettle, weigh 11 g of trisilanol heptaisobutyl polysilsesquioxane, 120 g of solvent, and 4 g of (methacryloyloxymethyl)methyldimethoxysilane, introduce nitrogen, and stir in a water bath to react;

[0048] S2: Continue to add 0.3g of isopropanol solution of chloroplatinic acid, then add 0.15g of vinylferrocene and 0.03g of lanthanum triammonium dimethylallyl diphosphate, stir and heat to react for 25 minutes, and then remove the solvent by distillation under reduced pressure;

[0049] S3: adding alcohol to wash repeatedly, and then drying in a vacuum oven to obtain polyhedral oligomeric silsesquioxane containing propenyl metallocene.

[0050] The solvent is selected from ethylene dichloride.

[0051] The water bath temperature in step S1 is 20°C.

[0052] The stirring speed of step S1 is 285 rpm, and the stirring reaction time is 16 h.

[0053] The vacuum degree of the vacuum oven in step S1 is not higher than 500 Pa, and the oven temperature is 45°C.

[0054] The reaction temperature of step S2 is 50°C

[0055] The mass percentage of the isopropanol solution of chloroplatinic acid in step S2 is 7%.

[0056] The alcohol in step S3 is selected from methanol.

[0057] The vacuum degree of the vacuum oven in step S3 is not higher than 600 Pa, and the oven temperature is 55°C.

[0058] Example 3

[0059] A method for preparing polyhedral oligomeric silsesquioxane containing propylene metallocene, characterized in that it comprises the following steps:

[0060] S1: In a reaction kettle, weigh 14 g of trisilanol heptaisobutyl polysilsesquioxane, 140 g of solvent, and 5 g of (methacryloyloxymethyl)methyldimethoxysilane, introduce nitrogen, and stir in a water bath to react;

[0061] S2: Continue to add 0.5g of isopropanol solution of chloroplatinic acid, then add 0.3g of vinylferrocene and 0.07g of lanthanum triammonium dimethylallyl diphosphate, stir and heat to react for 40 minutes, and then remove the solvent by distillation under reduced pressure;

[0062] S3: adding alcohol to wash repeatedly, and then drying in a vacuum oven to obtain polyhedral oligomeric silsesquioxane containing propenyl metallocene.

[0063] The solvent selected is methyl acetate.

[0064] The water bath temperature in step S1 is 24°C.

[0065] The stirring speed of step S1 is 385 rpm, and the stirring reaction time is 20 h.

[0066] The vacuum degree of the vacuum oven in step S1 is not higher than 500 Pa, and the oven temperature is 50°C.

[0067] The reaction temperature of step S2 is 60°C

[0068] The mass percentage of the isopropanol solution of chloroplatinic acid in step S2 is 9%.

[0069] The alcohol in step S3 is selected from ethanol.

[0070] The vacuum degree of the vacuum oven in step S3 is not higher than 600 Pa, and the oven temperature is 70°C.

[0071] Example 4

[0072] A method for preparing polyhedral oligomeric silsesquioxane containing propylene metallocene, characterized in that it comprises the following steps:

[0073] S1: In a reaction kettle, weigh 16 g of trisilanol heptaisobutyl polysilsesquioxane, 160 g of solvent, and 7 g of (methacryloyloxymethyl)methyldimethoxysilane, introduce nitrogen, and stir in a water bath to react;

[0074] S2: Continue to add 0.7g of isopropanol solution of chloroplatinic acid, then add 0.5g of vinylferrocene and 0.1g of lanthanum triammonium dimethylallyl diphosphate, stir and heat to react for 50 minutes, and then remove the solvent by distillation under reduced pressure;

[0075] S3: adding alcohol to wash repeatedly, and then drying in a vacuum oven to obtain polyhedral oligomeric silsesquioxane containing propenyl metallocene.

[0076] The solvent is dimethyl carbonate.

[0077] The water bath temperature in step S1 is 28°C.

[0078] The stirring speed of step S1 is 445 rpm, and the stirring reaction time is 24 h.

[0079] The vacuum degree of the vacuum oven in step S1 is not higher than 500 Pa, and the oven temperature is 60°C.

[0080] The reaction temperature of step S2 is 60°C

[0081] The mass percentage of the isopropanol solution of chloroplatinic acid in step S2 is 10%.

[0082] The alcohol in step S3 is selected from propanol.

[0083] The vacuum degree of the vacuum oven in step S3 is not higher than 600 Pa, and the oven temperature is 75°C.

[0084] Comparative Example 1

[0085] A method for preparing polyhedral oligomeric silsesquioxane containing propylene metallocene, characterized in that it comprises the following steps:

[0086] S1: In a reaction kettle, weigh 8 g of trisilanol heptaisobutyl polysilsesquioxane, 100 g of solvent, and 3 g of (methacryloyloxymethyl)methyldimethoxysilane, introduce nitrogen, and stir in a water bath to react;

[0087] S2: Continue to add 0.1g of isopropanol solution of chloroplatinic acid, then add 0.01g of dimethylallyl ammonium lanthanum diphosphate, stir and heat to react for 20 minutes, and then remove the solvent by distillation under reduced pressure;

[0088] S3: adding alcohol to wash repeatedly, and then drying in a vacuum oven to obtain polyhedral oligomeric silsesquioxane containing propenyl metallocene.

[0089] The solvent selected is dichloromethane.

[0090] The water bath temperature in step S1 is 16°C.

[0091] The stirring speed of step S1 is 185 rpm, and the stirring reaction time is 12 h.

[0092] The vacuum degree of the vacuum oven in step S1 is not higher than 500 Pa, and the oven temperature is 40°C.

[0093] The reaction temperature of step S2 is 50°C

[0094] The mass percentage of the isopropanol solution of chloroplatinic acid in step S2 is 5%.

[0095] The alcohol in step S3 is selected from methanol.

[0096] The vacuum degree of the vacuum oven in step S3 is not higher than 600 Pa, and the oven temperature is 50°C.

[0097] Comparative Example 2

[0098] A method for preparing polyhedral oligomeric silsesquioxane containing propylene metallocene, characterized in that it comprises the following steps:

[0099] S1: In a reaction kettle, weigh 8 g of trisilanol heptaisobutyl polysilsesquioxane, 100 g of solvent, and 3 g of (methacryloyloxymethyl)methyldimethoxysilane, introduce nitrogen, and stir in a water bath to react;

[0100] S2: Continue to add 0.1g of isopropanol solution of chloroplatinic acid, then add 0.03g of vinylferrocene, stir and heat to react for 20 minutes, then remove the solvent by distillation under reduced pressure;

[0101] S3: adding alcohol to wash repeatedly, and then drying in a vacuum oven to obtain polyhedral oligomeric silsesquioxane containing propenyl metallocene.

[0102] The solvent selected is dichloromethane.

[0103] The water bath temperature in step S1 is 16°C.

[0104] The stirring speed of step S1 is 185 rpm, and the stirring reaction time is 12 h.

[0105] The vacuum degree of the vacuum oven in step S1 is not higher than 500 Pa, and the oven temperature is 40°C.

[0106] The reaction temperature of step S2 is 50°C

[0107] The mass percentage of the isopropanol solution of chloroplatinic acid in step S2 is 5%.

[0108] The alcohol in step S3 is selected from methanol.

[0109] The vacuum degree of the vacuum oven in step S3 is not higher than 600 Pa, and the oven temperature is 50°C.

[0110] Evaluation of the embodiment:

[0111] 1. Thermal stability test: The polysilsesquioxane prepared in the above embodiment was subjected to TGA test;

[0112] 2. Corrosion resistance test: Referring to the national standard GB / T1771-91, Q235 steel was used as the substrate, and the polysilsesquioxane prepared in the above embodiment was sprayed, and the coating thickness was 150±5 μm. After fully drying, a neutral salt spray test was performed.

[0113] 3. Mechanical property test: The tensile strength test of the polysilsesquioxane prepared in the above example was carried out with reference to the national standard GB / T 16719-2008.

[0114] Table 4 Evaluation results of examples and comparative examples

[0115] Decomposition temperature when weight loss is 10% Corrosion resistance Tensile strength MPa Example 1 441.6 No gloss loss, no bubbles 12.2 Example 2 447.4 No gloss loss, no bubbles 14.5 Example 3 449.8 No gloss loss, no bubbles 17.1 Example 4 448.5 No gloss loss, no bubbles 16.6 Comparative Example 1 407.6 Slight loss of gloss, no bubbles 8.5 Comparative Example 2 411.8 Slight loss of gloss, no bubbles 9.1

[0116] The present invention has been described above through specific implementation methods and examples, but these descriptions are only illustrative and should not be understood as limiting the scope of protection of the present invention. Without departing from the spirit and scope of protection of the present invention, those skilled in the art may make various improvements, modifications or equivalent substitutions to the technical solutions and implementation methods of the present invention, all of which should fall within the scope of protection of the present invention.

Claims

1. A method for preparing a polyhedral oligomeric silsesquioxane containing an propylene metallocene, characterized in that: The steps include: S1: In a reaction kettle, weigh 8-16 parts of trisilanol heptaisobutyl polysilsesquioxane, 100-160 parts of solvent, and 3-7 parts of (methacryloyloxymethyl)methyldimethoxysilane, introduce nitrogen, and stir in a water bath to react; S2: Continue to add 0.1-0.7 parts of isopropanol solution of chloroplatinic acid, and then add 0.03-0.5 parts of vinylferrocene and 0.01-0.1 parts of dimethylallyl triammonium lanthanum diphosphate, stirring and heating to react for 20-50 minutes, and then remove the solvent by distillation under reduced pressure; S3: adding alcohol to wash repeatedly, and then drying in a vacuum oven to obtain polyhedral oligomeric silsesquioxane containing propenyl metallocene.

2. The method for preparing a polyhedral oligomeric silsesquioxane containing acryl metallocene according to claim 1, characterized in that: The solvent is selected from at least one of dichloromethane, dichloroethane, dichloropropane, methyl acetate, dimethyl carbonate or propylene glycol methyl ether acetate.

3. The method for preparing a polyhedral oligomeric silsesquioxane containing acryl metallocene according to claim 1, characterized in that: The water bath temperature in step S1 is 16-28°C.

4. The method for preparing a polyhedral oligomeric silsesquioxane containing acryl metallocene according to claim 1, characterized in that: The stirring speed of step S1 is 185-445 rpm, and the stirring reaction time is 12-24 h.

5. The method for preparing a polyhedral oligomeric silsesquioxane containing acryl metallocene according to claim 1, characterized in that: The vacuum degree of the vacuum oven in step S1 is not higher than 500 Pa, and the oven temperature is 40-60°C.

6. The method for preparing a polyhedral oligomeric silsesquioxane containing acryl metallocene according to claim 1, characterized in that: The reaction temperature of step S2 is 50-60°C.

7. The method for preparing a polyhedral oligomeric silsesquioxane containing acryl metallocene according to claim 1, characterized in that: The mass percentage of the isopropanol solution of chloroplatinic acid in step S2 is 5-10%.

8. The method for preparing a polyhedral oligomeric silsesquioxane containing acryl metallocene according to claim 1, characterized in that: The alcohol in step S3 is selected from at least one of methanol, ethanol or propanol.

9. The method for preparing a polyhedral oligomeric silsesquioxane containing acryl metallocene according to claim 1, characterized in that: The vacuum degree of the vacuum oven in step S3 is not higher than 600 Pa, and the oven temperature is 50-75°C.

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