A polyurethane composite material and its preparation method and application

Abstract

The present invention relates to a polyurethane composite material and a preparation method and application thereof, and belongs to the technical field of coatings. The polyurethane composite material provided by the present invention comprises the following components in parts by mass: 100 parts of polyether polyol, 15-60 parts of isocyanate, 2-10 parts of crosslinking agent, 0.05-2 parts of catalyst, 3-10 parts of chain extender, 0.5-8 parts of nano silicon carbide whisker, 1-5 parts of foaming agent, and 0.2-2 parts of foam stabilizer; the hydroxyl value of the polyether polyol is 17-40 mg KOH / g; the isocyanate comprises lysine diisocyanate and isophorone diisocyanate. The polyurethane composite material provided by the present invention has excellent tensile strength and tear strength, and the obtained polyurethane composite material also has excellent heat resistance. At the same time, the raw material source of the polyurethane composite material provided by the present invention is wide, the preparation method is simple to operate, and is conducive to actual production.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to a polyurethane composite material and a preparation method and application thereof. Background Art

[0002] Polyurethane is a polymer material formed by polycondensation of polyols and polyisocyanates. There are many types of polyurethane, including polyether, polyester, polyimide, and polyurea. All types of polyurethane can be used to prepare polyurethane plastics, polyurethane fibers, polyurethane rubbers, and elastomers. Polyurethane can also be used to make adhesives, coatings, synthetic leather, etc.

[0003] Therefore, polyurethane has different applications in various industries in real life; in the process of application, how to provide a polyurethane material with excellent mechanical properties and good temperature stability is a widely pursued goal. Summary of the invention

[0004] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a polyurethane composite material with excellent mechanical properties and excellent heat resistance.

[0005] To achieve the above object, in a first aspect of the present invention, the present invention provides a polyurethane composite material, the polyurethane composite material comprising the following components in parts by weight: 100 parts of polyether polyol, 15-60 parts of isocyanate, 2-10 parts of crosslinking agent, 0.05-2 parts of catalyst, 3-10 parts of chain extender, 0.5-8 parts of nano silicon carbide whisker, 1-5 parts of foaming agent, and 0.2-2 parts of foam stabilizer;

[0006] The hydroxyl value of the polyether polyol is 17-40 mg KOH / g;

[0007] The isocyanate includes lysine diisocyanate and isophorone diisocyanate.

[0008] The polyurethane composite material provided by the present invention has excellent tensile strength and tear strength and also excellent heat resistance by selecting components in appropriate mass parts and the components cooperate with each other.

[0009] Specifically, on the one hand, in the preparation process of polyurethane, the hydroxyl value range of the polyether polyol in the raw material will affect the number of cross-linking points and the number of carbon skeletons in the prepared polyurethane molecular chain, and will also affect the segment space in the prepared polyurethane composite material, that is, the pore size between molecules; on the other hand, different types of isocyanates represent different structures, which will not only affect the activity during the reaction, but also affect the type of chain segments after the reaction, thereby affecting the interaction between the molecular groups of the product, such as affecting the number or strength of intermolecular hydrogen bonds, and further affecting the mechanical properties and heat resistance of the product; on the third hand, nano-silicon carbide whiskers can also further help improve the mechanical properties and heat resistance stability of the polyurethane composite material; on the fourth hand, by selecting a polyether polyol within a specific hydroxyl value range and a specific type of isocyanate in the present invention for compounding, and adding a specific mass portion of nano-silicon carbide whiskers and a chain extender, a polyurethane composite material with excellent comprehensive performance can be obtained.

[0010] As a preferred embodiment of the polyurethane combination material of the present invention, the polyurethane combination material includes the following components in parts by mass: 100 parts of polyether polyol, 20-30 parts of isocyanate, 4-6 parts of cross-linking agent, 0.1-0.5 parts of catalyst, 5-8 parts of chain extender, 2-4 parts of nano silicon carbide whiskers, 2-3 parts of foaming agent, and 0.5-1 parts of foam stabilizer.

[0011] The present invention has found that the mass parts of the components of the polyurethane combination material will affect the performance of the product. When the mass parts of the polyurethane combination material are further selected to be within the above preferred range, the obtained polyurethane combination material has higher tensile strength and tear strength, and better heat resistance.

[0012] As a preferred embodiment of the polyurethane composition of the present invention, the polyether polyols include HSH-240 and HSH-230.

[0013] The present invention has found that the specific type of polyether polyol selected will also affect the performance of the product. When the polyether polyols HSH-240 and HSH-230 are further selected, the comprehensive performance of the obtained product is better.

[0014] As a preferred embodiment of the polyurethane composition of the present invention, the mass ratio of HSH-240 to HSH-230 is 1:(1.5-2).

[0015] Exemplarily, the mass ratio of HSH-240 to HSH-230 may be any point value or any range value between 1:(1.5-2), such as 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, etc.

[0016] The present invention has found that when the selected polyether polyols are HSH-240 and HSH-230, the mass ratio between HSH-240 and HSH-230 will also affect the mechanical properties and heat resistance of the prepared polyurethane composite material. When the mass ratio of HSH-240 and HSH-230 is further selected to be 1:(1.5-2), the comprehensive performance of the obtained product is better.

[0017] As a preferred embodiment of the polyurethane composition of the present invention, the mass ratio of the lysine diisocyanate to the isophorone diisocyanate is 1:(0.2-0.8).

[0018] Exemplarily, the mass ratio of lysine diisocyanate to isophorone diisocyanate may be any point value or any range value between 1:(0.2-0.8), such as 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, etc.

[0019] The present invention has found that when lysine diisocyanate and isophorone diisocyanate are used as isocyanates for the reaction at the same time, the mass ratio of the two will significantly affect the mechanical properties of the prepared polyurethane composite material, and also has a certain influence on the heat resistance of the polyurethane composite material. When the mass ratio of lysine diisocyanate and isophorone diisocyanate is further selected to be 1: (0.2-0.8), the comprehensive performance of the obtained product is better.

[0020] As a preferred embodiment of the polyurethane composition of the present invention, the average aspect ratio of the nano-silicon carbide whiskers is 50-150.

[0021] For example, the average aspect ratio of the nano-silicon carbide whiskers may be 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, etc.

[0022] The present invention has found that the average aspect ratio of nano-silicon carbide whiskers will affect the comprehensive performance of the product. When the average aspect ratio of the nano-silicon carbide whiskers is further selected to be within the range given by the present invention, on the one hand, the problem that the average aspect ratio of the nano-silicon carbide whiskers is too small and the mechanical properties and heat resistance of the product are not significantly improved can be avoided. On the other hand, the problem that the average aspect ratio of the nano-silicon carbide whiskers is too large and causes damage to the mechanical properties and heat resistance of the product can also be avoided.

[0023] As a preferred embodiment of the polyurethane composition of the present invention, the chain extender includes at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, diethylene glycol, and dipropylene glycol.

[0024] Preferably, the chain extender comprises 1,4-butanediol.

[0025] The present invention has found that the selection of chain extender will also affect the comprehensive performance of the polyurethane composite material. When 1,4-butanediol is further selected as the chain extender, the mechanical properties of the obtained product are better, and the heat resistance shows a certain upward trend.

[0026] As a preferred embodiment of the polyurethane composition of the present invention, the crosslinking agent includes at least one of triethanolamine, diethanolamine and glycerol.

[0027] Preferably, the cross-linking agent is glycerol.

[0028] As a preferred embodiment of the polyurethane composition of the present invention, the catalyst includes at least one of an organic tin catalyst and an organic bismuth catalyst.

[0029] Illustratively, the organotin catalyst includes at least one of tetraphenyltin, stannous octoate, and dibutyltin dilaurate; the organobismuth catalyst includes at least one of bismuth cyclohexaneate, bismuth isooctanoate, and bismuth laurate.

[0030] As a preferred embodiment of the polyurethane composition of the present invention, the foaming agent includes water.

[0031] As a preferred embodiment of the polyurethane composition of the present invention, the foam stabilizer includes a polysiloxane-polyether copolymer.

[0032] In a second aspect of the present invention, the present invention provides a method for preparing a polyurethane composition, the preparation method comprising the following steps:

[0033] (1) mixing a polyether polyol, a cross-linking agent, a catalyst, a chain extender, nano silicon carbide whiskers, a foaming agent, and a foam stabilizer to obtain component A;

[0034] (2) using isocyanate as component B;

[0035] (3) Component A and component B are sealed and stored separately to obtain a polyurethane composite material.

[0036] In the third aspect of the present invention, the present invention also provides a method for using the polyurethane composite material, the method comprising the following steps: mixing component A and component B evenly under high pressure, then spraying them in atomized form and rapidly foaming them to obtain a polyurethane foam material. For example, using a pneumatic airless sprayer, injecting component A and component B into a spray gun respectively, mixing them evenly in a mixing chamber under high pressure, then spraying them in atomized form and rapidly foaming them to obtain a polyurethane foam material.

[0037] In a fourth aspect of the present invention, the present invention provides a use of the polyurethane composition in preparing a coating.

[0038] The polyurethane composite material provided by the present invention has excellent mechanical properties and heat resistance, and can be well applied to the preparation of coatings by adopting a foaming molding method.

[0039] Compared with the prior art, the present invention has the following advantages:

[0040] The polyurethane composite material provided by the present invention has excellent tensile strength and tear strength by selecting components of appropriate mass parts, and the components cooperate with each other, and the obtained polyurethane composite material also has excellent heat resistance. At the same time, the raw material source of the polyurethane composite material provided by the present invention is wide, and the preparation method is simple to operate, which is conducive to actual production. DETAILED DESCRIPTION

[0041] To better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific examples. Other materials, reagents, etc. used in the examples, unless otherwise specified, can be obtained from commercial sources.

[0042] Polyether polyol 1: HSH-240, hydroxyl value about 28 mg KOH / g, Huaian Petrochemical Plant, Jiangsu Province;

[0043] Polyether polyol 2: HSH-230, hydroxyl value about 38 mg KOH / g, Huaian Petrochemical Plant, Jiangsu Province;

[0044] Polyether polyol 3: HSH-260, hydroxyl value about 18 mg KOH / g, Huaian Petrochemical Plant, Jiangsu Province;

[0045] Polyether polyol 4: HSH-220, hydroxyl value about 56 mg KOH / g, Huaian Petrochemical Plant, Jiangsu Province;

[0046] Polyether polyol 5: HSH-280, hydroxyl value about 14 mg KOH / g, Huaian Petrochemical Plant, Jiangsu Province;

[0047] Polyether polyol 6: KDF, hydroxyl value is about 39mg KOH / g, Tianjin Petrochemical Plant No. 3;

[0048] Nano silicon carbide whisker 1: SiC-150, average aspect ratio is about 150, Yamei nanometer;

[0049] Nano silicon carbide whisker 2: SiC-50, average aspect ratio of about 50, Yamei nanometer;

[0050] Nano silicon carbide whisker 3: SiC-250, average aspect ratio of about 250, Yamei nanometers;

[0051] Nano silicon carbide whisker 4: SiC-20, average aspect ratio is about 20, Yamei nanometer;

[0052] Nano titanium dioxide whiskers: TiO 2 -NW-15, average aspect ratio of about 150, Stellite metal;

[0053] Isocyanate 1: lysine diisocyanate, LDI, commercially available;

[0054] Isocyanate 2: isophorone diisocyanate, IPDI, commercially available;

[0055] Isocyanate 3: hexamethylene dicyanate, HDI, commercially available;

[0056] Cross-linking agent: glycerol, commercially available;

[0057] Catalyst: bismuth laurate, commercially available;

[0058] Chain extender 1: 1,4-butanediol, commercially available;

[0059] Chain extender 2: 1,3-propylene glycol, commercially available;

[0060] Foam stabilizer: HY-193, Shanghai Huiyan New Materials Co., Ltd.

[0061] Examples 1-13 and Comparative Examples 1-8

[0062] The embodiments and comparative examples of the present invention provide a polyurethane composition, the components (in parts by mass) of the polyurethane composition are shown in Table 1-2;

[0063] Table 1

[0064]

[0065]

[0066] Table 2

[0067]

[0068] The preparation method of the polyurethane composite material provided in Example 1 is:

[0069] (1) adding a polyether polyol, a crosslinking agent, a catalyst, a chain extender, nano-silicon carbide whiskers, a foaming agent, and a foam stabilizer into a reaction kettle, and stirring and mixing them uniformly at room temperature to obtain component A;

[0070] (2) using isocyanate as component B;

[0071] (3) injecting component A and component B into the spray gun of a pneumatic airless sprayer respectively, mixing them evenly in a mixing chamber under high pressure, and then spraying them out in atomized form at low pressure and rapidly foaming them to form a layer of continuous, dense and seamless polyurethane foam material, thereby obtaining a polyurethane composite material;

[0072] The preparation methods of Examples 2-13 and Comparative Examples 1-8 are consistent with that of Example 1, except that no relevant components are added.

[0073] Effect example

[0074] The effect examples of the present invention verify the performance of the polyurethane composite materials prepared by Examples 1-13 and Comparative Examples 1-8, including the following aspects:

[0075] 1) Tensile strength: Tested in accordance with GB / T 528-2009;

[0076] 2) Tear strength: Tested in accordance with GB / T 529-2008;

[0077] 3) Heat resistance: Tested in accordance with GB / T 3512-2001; test temperature 70°C, test time 96h; change rate of tensile strength as a means of characterizing heat resistance, tensile strength change rate = (tensile strength before heat test - tensile strength after heat test) / tensile strength before heat test × 100%;

[0078] The results obtained are shown in Table 3;

[0079] Table 3

[0080]

[0081]

[0082] It can be seen from Table 3 that when the technical solution provided by the present invention is adopted, the obtained product has excellent mechanical properties and heat resistance. Specifically, the obtained product has a tensile strength of more than 11.6 MPa, a tear strength of more than 46 kN / m, and a tensile strength change rate of more than 81%;

[0083] It can be seen from Example 1 and Comparative Examples 1-2 that the mass fraction of the components of the polyurethane composite material will have a significant effect on the product performance. When the mass fraction of the components in Comparative Examples 1-2 is not within the given range, compared with Example 1, the tensile strength of the obtained product decreases by 38.16-53.29%, the tear strength decreases by 38.46-56.92%, and the tensile strength change rate decreases by 26.32-34.74%; it can be seen from Example 1 and Comparative Examples 3-4 that the hydroxyl value of the polyether polyol will also affect the performance of the product. When the hydroxyl value of the polyether polyol in Comparative Examples 3-4 is not within the given range of the present invention, compared with Example 1, the tensile strength of the product obtained in Comparative Examples 3-4 decreases by 35.53-57.24%, the tear strength decreases by 35.38-60.00%, and the tensile strength change rate decreases by 25.26-28.42%; It can be seen from Example 1 and Comparative Examples 5-6 that the type of isocyanate will also affect the performance of the product. When the type of isocyanate selected in Comparative Examples 5-6 is not within the scope given in the present invention, compared with Example 1, the tensile strength of the product obtained in Comparative Examples 5-6 decreased by 44.74-52.63%, the tear strength decreased by 46.15-55.38%, and the tensile strength change rate decreased by 43.16-46.32%; it can be seen from Example 1 and Comparative Example 7 that the addition of nano-silicon carbide whiskers can better improve the comprehensive performance of the product; it can be seen from Example 1 and Comparative Example 8 that when other similar substances are used to replace nano-silicon carbide whiskers, the corresponding effect of the present invention cannot be achieved. Compared with Example 1, the tensile strength of the product obtained in Comparative Example 8 decreased by 38.82%, the tear strength decreased by 38.46%, and the tensile strength change rate decreased by 21.05%.

[0084] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A polyurethane composite material, characterized in that: The polyurethane composite material comprises the following components in parts by weight: 100 parts of polyether polyol, 15-60 parts of isocyanate, 2-10 parts of crosslinking agent, 0.05-2 parts of catalyst, 3-10 parts of chain extender, 0.5-8 parts of nano silicon carbide whisker, 1-5 parts of foaming agent, and 0.2-2 parts of foam stabilizer; The hydroxyl value of the polyether polyol is 17-40 mg KOH / g; The isocyanate comprises lysine diisocyanate and isophorone diisocyanate; the mass ratio of the lysine diisocyanate to isophorone diisocyanate is 1:(0.2-0.8).

2. The polyurethane composite material according to claim 1, characterized in that: The polyurethane composite material comprises the following components in parts by weight: 100 parts of polyether polyol, 20-30 parts of isocyanate, 4-6 parts of crosslinking agent, 0.1-0.5 parts of catalyst, 5-8 parts of chain extender, 2-4 parts of nano silicon carbide whiskers, 2-3 parts of foaming agent and 0.5-1 parts of foam stabilizer.

3. The polyurethane composite material according to claim 1, characterized in that: The polyether polyols include HSH-240 and HSH-230.

4. The polyurethane composite material according to claim 3, characterized in that: The mass ratio of HSH-240 to HSH-230 is 1:(1.5-2).

5. The polyurethane composite material according to claim 1, characterized in that: The average aspect ratio of the nano silicon carbide whiskers is 50-150.

6. The polyurethane composite material according to claim 1, characterized in that: The chain extender includes at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, diethylene glycol, and dipropylene glycol.

7. The polyurethane composition according to claim 1, characterized in that: Satisfy at least one of the following: a. The cross-linking agent includes at least one of triethanolamine, diethanolamine and glycerol; b. The catalyst includes at least one of an organic tin catalyst and an organic bismuth catalyst; c. The foaming agent includes water; d. The foam stabilizer comprises a polysiloxane-polyether copolymer.

8. The method for preparing the polyurethane composition according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: (1) mixing a polyether polyol, a cross-linking agent, a catalyst, a chain extender, nano silicon carbide whiskers, a foaming agent, and a foam stabilizer to obtain component A; (2) using isocyanate as component B; (3) Component A and component B are sealed and stored separately to obtain a polyurethane composite material.

9. Use of the polyurethane combination as claimed in any one of claims 1 to 7 in the preparation of coatings.

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