Silicon-zirconium synergistically modified polyurethane used as wall and floor coating and preparation method of silicon-zirconium synergistically modified polyurethane

Abstract

The invention belongs to the technical field of polyurethane, and particularly relates to silicon-zirconium synergistically modified polyurethane used as a wall and floor coating and a preparation method of the silicon-zirconium synergistically modified polyurethane. The silicon-zirconium synergetic modified polyurethane used as the wall and floor coating is prepared by mixing zirconium-silicon-containing polyurethane and amino polysilane, molecular main chains of the zirconium-silicon-containing polyurethane and the amino polysilane contain zirconium and silicon which are combined in a covalent bond mode, the intrinsic thermal stability of the polyurethane is improved, and meanwhile the compatibility of the zirconium-silicon-containing polyurethane and the amino polysilane can be improved through a similar structure. In the curing process of the silicon-zirconium synergetic modified polyurethane used as the wall and floor coating, an interpenetrating polymer network can be formed through hydrogen bonds, amino groups and a curing agent, and the flexibility of the polymer network is improved by optimizing the dosage of the curing agent, so that the thermal stability of the silicon-zirconium synergetic modified polyurethane used as the wall and floor coating is improved, and the service life of the silicon-zirconium synergetic modified polyurethane used as the wall and floor coating is prolonged. The problem of embrittlement of the coating caused by overhigh crosslinking density is avoided, and the toughness of the coating is ensured.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane, and in particular relates to a silicon-zirconium synergistically modified polyurethane used as a wall and floor coating and a preparation method thereof. Background Art

[0002] Polyurethane materials have many advantages, including light weight, wear resistance, oil resistance, low temperature resistance, aging resistance, high hardness and good elasticity. These characteristics make polyurethane materials widely used in many fields, such as textiles, construction, aviation, shipping, transportation, medicine and electronics. Although polyurethane materials have many excellent properties, they are prone to degradation in high temperature environments, which limits their application in some fields with high thermal stability requirements, especially for wall and floor coatings in high temperature industrial environments.

[0003] Methods to improve the thermal stability of polyurethane include adding fillers with high thermal stability (such as flame retardants, carbon nanotubes, etc.), increasing the crosslinking degree of polyurethane, silicone modification, etc. The addition of fillers and silicone modification often face compatibility issues, which will affect the modification effect and even cause adverse phenomena such as phase separation inside the material. The increase in crosslinking density will make the material lack sufficient flexibility and weaken its toughness, resulting in cracking when subjected to external impact, affecting its service life and protective effect. At present, it is difficult to improve the thermal stability of polyurethane while ensuring that other properties are not affected. Summary of the invention

[0004] In view of the shortcomings of the existing methods, the technical solution adopted by the present invention is: the present invention provides a silicon-zirconium synergistically modified polyurethane used as a wall and floor coating, and the polyurethane is composed of the following raw materials: zirconium-containing silicon polyurethane and aminopolysilane.

[0005] Furthermore, the zirconium-silicon-containing polyurethane is prepared by reacting polyethylene glycol, cyclopentadienyl zirconium trichloride, chlorosilane and isocyanate compound.

[0006] Preferably, the molecular weight of the polyethylene glycol is 200-2000.

[0007] Preferably, the chlorosilane includes one or more of diphenyldichlorosilane, dimethyldichlorosilane, and dichlorodiethylsilane.

[0008] Preferably, the isocyanate compound includes one or more of o-xylylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and triphenylmethane triisocyanate.

[0009] Furthermore, the aminopolysilane is prepared by reacting silane, aminosilane, zirconium oxychloride and hexamethyldisiloxane.

[0010] Preferably, the silane includes one or more of methyldiethoxysilane and methyldimethoxysilane.

[0011] Preferably, the aminosilane includes one or more of N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane and aminopropylmethyldiethoxysilane.

[0012] The preparation method of the silicon-zirconium synergistically modified polyurethane used as wall and floor coating comprises the following steps:

[0013] (1) Preparation of zirconium-silicon-containing polyurethane: polyethylene glycol is mixed with tetrahydrofuran, and then triethylamine is added to react at 0-8°C for 10-12 hours, and a mixed solution of cyclopentadienyl zirconium trichloride and chlorosilane is added dropwise, mixed evenly, and then added dropwise to the reaction solution; then an isocyanate compound is added, and the reaction is continued at 55-80°C for 8-13 hours; after the reaction is completed, the reaction is filtered, and the filtrate is rotary evaporated to obtain zirconium-silicon-containing polyurethane.

[0014] Preferably, the molar ratio of polyethylene glycol to triethylamine is 1:0.8-1.1.

[0015] Preferably, the molar ratio of the polyethylene glycol, cyclopentadienyl zirconium trichloride, chlorosilane and isocyanate compound is 1: 0.01-0.04: 0.01-0.04: 0.2-0.3.

[0016] (2) Preparation of aminopolysilane: First, silane and zirconium oxychloride were mixed and stirred evenly, and then aminosilane was added; under the action of magnetic stirring, distilled water was added dropwise into the beaker for hydrolysis-copolymerization reaction, and stirred for 30-50 minutes, hexamethyldisiloxane was added, and the stirring reaction was continued for 30 minutes, and washed with water until neutral, and water and ethanol were evaporated by reduced pressure distillation to obtain aminopolysilane.

[0017] Preferably, the molar ratio of the silane, zirconium oxychloride, aminosilane and hexamethyldisiloxane is 1-3: 0.1-0.3: 0.7-1.0: 0.1-0.4.

[0018] Preferably, the ratio of distilled water to silane is 0.8-1 mL: 0.01 mol.

[0019] (3) Preparation of silicon-zirconium synergistically modified polyurethane for wall and floor coatings: Zirconium-containing silicon polyurethane and aminopolysilane are mixed to prepare silicon-zirconium synergistically modified polyurethane for wall and floor coatings.

[0020] Preferably, the mass ratio of the zirconium-silicon-containing polyurethane to the aminopolysilane is 1:0.1-0.4.

[0021] The above-mentioned silicon-zirconium synergistically modified polyurethane used as wall and floor coating can be used to make coatings, which include the following raw materials: silicon-zirconium synergistically modified polyurethane used as wall and floor coatings, and a curing agent; the mass ratio of the silicon-zirconium synergistically modified polyurethane used as wall and floor coatings and the curing agent is 100:4-8.

[0022] Preferably, the curing agent is a polyepoxy compound, including one or more of ethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, and glycidyl ether.

[0023] The beneficial effects of the present invention are:

[0024] The silicon-zirconium synergistically modified polyurethane used as wall and floor coatings of the present invention is prepared by mixing zirconium-containing silicon polyurethane and aminopolysilane. The main molecular chain of the zirconium-containing silicon polyurethane contains zirconium and silicon (Zr-OC, Zr-O-Si, Si-OC, etc.) bound in the form of covalent bonds, which improves the intrinsic thermal stability of the polyurethane; the molecular chain of the aminopolysilane contains zirconium and silicon bound in the form of covalent bonds similar to the zirconium-containing silicon polyurethane, so that it has good compatibility with the zirconium-containing silicon polyurethane; during the curing process, the silicon-zirconium synergistically modified polyurethane used as wall and floor coatings can form an interpenetrating polymer network with the curing agent through hydrogen bonds and amino groups, and the flexibility of the polymer network is improved by optimizing the amount of the curing agent, while improving the thermal stability of the silicon-zirconium synergistically modified polyurethane used as wall and floor coatings, avoiding the problem of coating embrittlement caused by excessive crosslinking density, and ensuring its toughness. DETAILED DESCRIPTION

[0025] The present invention will be further described below in conjunction with the embodiments.

[0026] Embodiment 1:

[0027] (1) Preparation of zirconium-containing silicon polyurethane: 0.1 mol of polyethylene glycol (PEG200) was mixed with 100 mL of tetrahydrofuran, and then 0.1 mol of triethylamine was added to react at 3-6°C for 12 h, and a mixture of 0.01 mol of cyclopentadienyl zirconium trichloride and 0.04 mol of dimethyldichlorosilane was added dropwise, mixed evenly, and then added dropwise to the reaction solution; then 0.02 mol of isophorone diisocyanate was added, and the reaction was continued at 60°C for 12 h; after the reaction was completed, the mixture was filtered and the filtrate was rotary evaporated to obtain zirconium-containing silicon polyurethane.

[0028] (2) Preparation of aminopolysilane: First, 0.1 mol of methyldimethoxysilane and 0.02 mol of zirconium oxychloride were mixed and stirred evenly, and then 0.07 mol of aminopropylmethyldiethoxysilane was added; under the action of magnetic stirring, 8 mL of distilled water was added dropwise into the beaker for hydrolysis-copolymerization reaction, and stirred for 30 minutes, and 0.02 mol of hexamethyldisiloxane was added, and the stirring reaction was continued for 30 minutes, and washed with water until neutral, and water and ethanol were evaporated by reduced pressure distillation to obtain aminopolysilane.

[0029] (3) Preparation of silicon-zirconium synergistically modified polyurethane for wall and floor coatings: Zirconium-containing silicon polyurethane and aminopolysilane are mixed in a mass ratio of 1:0.3 to obtain silicon-zirconium synergistically modified polyurethane for wall and floor coatings.

[0030] Embodiment 2:

[0031] The difference between Example 2 and Example 1 is that in step (3), the mass ratio of zirconium-silicon polyurethane to aminopolysilane is 1:0.1, and the rest is the same as Example 1.

[0032] Embodiment 3:

[0033] The difference between Example 3 and Example 1 is that in step (3), the mass ratio of zirconium-silicon polyurethane to aminopolysilane is 1:0.2, and the rest is the same as Example 1.

[0034] Embodiment 4:

[0035] The difference between Example 4 and Example 1 is that in step (1), a mixed solution consisting of 0.02 mol of cyclopentadienyl zirconium trichloride and 0.03 mol of dimethyldichlorosilane is added dropwise, and the rest is the same as in Example 1.

[0036] Embodiment 5:

[0037] The difference between Example 5 and Example 1 is that in step (1), a mixed solution consisting of 0.03 mol of cyclopentadienyl zirconium trichloride and 0.02 mol of dimethyldichlorosilane is added dropwise, and the rest is the same as in Example 1.

[0038] Embodiment 6:

[0039] The difference between Example 5 and Example 1 is that in step (1), a mixed solution consisting of 0.04 mol of cyclopentadienyl zirconium trichloride and 0.01 mol of dimethyldichlorosilane is added dropwise, and the rest is the same as in Example 1.

[0040] Example 7

[0041] The difference between Example 7 and Example 1 is that in step (3), the mass ratio of zirconium-silicon polyurethane to aminopolysilane is 1:0.4, and the rest is the same as Example 1.

[0042] Comparative Example 1

[0043] The difference between Comparative Example 1 and Example 1 is that in step (3), the mass ratio of zirconium-silicon polyurethane to aminopolysilane is 1:0, and the rest is the same as Example 1.

[0044] Comparative Example 2

[0045] The difference between Comparative Example 2 and Example 1 is that in step (1), a mixed solution consisting of 0 mol of cyclopentadienyl zirconium trichloride and 0.05 mol of dimethyldichlorosilane is added dropwise, and the rest is the same as Example 1.

[0046] Effect Example 1

[0047] The polyurethane prepared in the above examples and comparative examples was mixed with ethylene glycol diglycidyl ether, introduced into a mold, cured at 100°C / 4h+130°C / 4h, and the impact strength (original, 300°C / 2h pretreatment) and fracture toughness were tested according to ASTM D256-10 and GB / T2567-2021. The test results are shown in Table 1. The mass ratio of the polyurethane to ethylene glycol diglycidyl ether is 100:6.

[0048] Table 1

[0049]

[0050] Effect Example 2

[0051] The polyurethane prepared in Example 5 was mixed with ethylene glycol diglycidyl ether ammonia in a mass ratio of 100:4-8, introduced into a mold, and cured at 100°C / 4h+130°C / 4h. The impact strength and hardness were tested according to ASTM D256-10 and ASTM D2240. The results are shown in Table 2.

[0052] Table 2

[0053] Mass ratio of polyurethane to ethylene glycol diglycidyl ether ammonia Surface hardness <![CDATA[Impact strength (KJ / m -2 )]]> 100：4 63 72 100：6 71 79 100：8 77 67 100：10 82 56

[0054] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A silicon-zirconium synergistically modified polyurethane for use as a wall and floor coating, characterized in that: The polyurethane consists of zirconium-silicon-containing polyurethane and aminopolysilane.

2. The silicon-zirconium synergistically modified polyurethane used as wall and floor coating according to claim 1, characterized in that: The mass ratio of the zirconium-silicon-containing polyurethane to the aminopolysilane in the polyurethane is 1:0.1-0.

4.

3. The silicon-zirconium synergistically modified polyurethane used as wall and floor coating according to claim 1, characterized in that: The zirconium-silicon-containing polyurethane is prepared by reacting polyethylene glycol, cyclopentadienyl zirconium trichloride, chlorosilane and isocyanate compound; The chlorosilane includes one or more of diphenyldichlorosilane, dimethyldichlorosilane, and dichlorodiethylsilane; The isocyanate compound includes one or more of o-xylylene diisocyanate, m-xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and triphenylmethane triisocyanate.

4. The silicon-zirconium synergistically modified polyurethane used as wall and floor coating according to claim 1, characterized in that: The aminopolysilane is prepared by reacting silane, aminosilane, zirconium oxychloride and hexamethyldisiloxane; The silane includes one or more of methyldiethoxysilane and methyldimethoxysilane; The aminosilane includes one or more of N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane and aminopropylmethyldiethoxysilane.

5. A method for preparing the silicon-zirconium synergistically modified polyurethane used as wall and floor coating according to claim 1, characterized in that: The following steps are involved: (1) Preparation of zirconium-silicon-containing polyurethane: polyethylene glycol and tetrahydrofuran are mixed, and then triethylamine is added to react at 0-8°C for 10-12 hours, and a mixed solution of cyclopentadienyl zirconium trichloride and chlorosilane is added dropwise, mixed evenly, and then added dropwise to the reaction solution; then an isocyanate compound is added, and the reaction is continued at 55-80°C for 8-13 hours; after the reaction is completed, the reaction is filtered, and the filtrate is subjected to rotary evaporation to obtain zirconium-silicon-containing polyurethane; (2) Preparation of aminopolysilane: First, silane and zirconium oxychloride were mixed and stirred evenly, and then aminosilane was added; under the action of magnetic stirring, distilled water was added dropwise to the beaker for hydrolysis-copolymerization reaction, and stirred for 30-50 minutes, hexamethyldisiloxane was added, and the stirring reaction was continued for 30 minutes, and the mixture was washed with water until neutral, and water and ethanol were evaporated by reduced pressure distillation to obtain aminopolysilane; (3) Preparation of silicon-zirconium synergistically modified polyurethane for wall and floor coatings: Zirconium-containing silicon polyurethane and aminopolysilane are mixed to prepare silicon-zirconium synergistically modified polyurethane for wall and floor coatings.

6. The method for preparing the silicon-zirconium synergistically modified polyurethane for wall and floor coating according to claim 5, characterized in that: The molar ratio of polyethylene glycol to triethylamine in step (1) is 1:0.8-1.1; The molar ratio of the polyethylene glycol, cyclopentadienyl zirconium trichloride, chlorosilane and isocyanate compound is 1: 0.01-0.04: 0.01-0.04: 0.2-0.

3.

7. The method for preparing the silicon-zirconium synergistically modified polyurethane for wall and floor coating according to claim 5, characterized in that: The molar ratio of silane, zirconium oxychloride, aminosilane and hexamethyldisiloxane in step (2) is 1-3: 0.1-0.3: 0.7-1.0: 0.1-0.4; The ratio of distilled water to silane is 0.8-1 mL: 0.01 mol.

8. The method for preparing the silicon-zirconium synergistically modified polyurethane for wall and floor coating according to claim 5, characterized in that: The mass ratio of the zirconium-silicon-containing polyurethane to the aminopolysilane in step (3) is 1:0.1-0.

4.

9. An application of the silicon-zirconium synergistically modified polyurethane as a wall and floor coating according to claim 1, characterized in that: The coating is used to make the coating; the coating comprises the following raw materials: silicon-zirconium synergistically modified polyurethane used as wall and floor coating, and a curing agent; the mass ratio of the silicon-zirconium synergistically modified polyurethane used as wall and floor coating to the curing agent is 100:4-8.

10. The use according to claim 9, characterized in that: The curing agent includes one or more of ethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, and glycidyl ether.

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