One-component low-viscosity and high weather-resistant spray surface material, its preparation method and application

Abstract

The present invention belongs to the technical field of polyurethane spray surface materials, and specifically relates to a one-component low-viscosity and high-weather-resistant spray surface material, its preparation method and application. The one-component low-viscosity and high-weather-resistant spray surface material includes the following raw materials: polyether polyol, isocyanate, reactive pigment, filler, dispersant, catalyst, ultraviolet absorber, antioxidant; when preparing the one-component low-viscosity and high-weather-resistant spray surface material, a dispersant is added to the polyether polyol, stirred evenly, then the pigment and filler are added, stirred evenly, dehydrated, and then the isocyanate, ultraviolet absorber and antioxidant are added for prepolymerization, and finally the temperature is lowered and the catalyst is added to obtain. The one-component low-viscosity and high-weather-resistant spray surface material of the present invention has the characteristics of environmental protection, low viscosity, excellent mechanical properties and high weather resistance. When it is applied to the runway spray surface layer, the construction is simple, the color is beautiful, and it is not easy to fade or lose color; the present invention also provides its preparation method.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyurethane spray surface materials, and particularly relates to a one-component low-viscosity and high-weather-resistant spray surface material, a preparation method thereof, and an application thereof. Background Art

[0002] The plastic runway is made of polymer materials and has the characteristics of high comfort, beautiful color, low maintenance cost, good elasticity, wear resistance, anti-slip, etc., providing an ideal sports venue for athletes. The plastic runway is not only widely used in various schools, stadiums and other places, but also becomes one of the standard venues for international track and field competitions. However, there are also many problems with plastic runways. First of all, most spray surface materials are two-component materials. When in use, the adhesive and color paste need to be matched on site, resulting in inaccurate addition of color paste and inconsistent site colors. Secondly, the viscosity of the material becomes larger at low temperatures (≤15°C), making on-site construction difficult. Finally, the weather resistance of the site is insufficient, and fading and color loss are likely to occur after long-term use.

[0003] Patent CN106118429A discloses a solvent-free one-component self-texturing material and a preparation method thereof. This material is a one-component product and does not require on-site mixing of materials. The product can be sprayed on the polished plastic bottom layer. However, the pigment used in this patent is iron oxide red, which belongs to a dispersed pigment. As the spray surface material ages, the pigment will gradually fade and lose color, affecting the use effect of the site.

[0004] In addition, to improve the weather resistance of plastic runways, a part of toluene diisocyanate (TDI) is usually added to the raw materials to replace diphenylmethane diisocyanate (MDI-50) with relatively poor weather resistance. Patent CN109651594A discloses a high-strength weather-resistant self-texturing material and a preparation method thereof. Toluene diisocyanate is introduced into the formula and rationally matched with aliphatic isocyanate, which prolongs the operation time, improves the mechanical properties of the product, improves the weather resistance of the product, and the fading and color loss of the product are improved. However, it uses two components, and when constructing, components A and B need to be mixed evenly before use, which has risks such as inconsistent site colors caused by uneven mixing. Secondly, when using toluene diisocyanate, the smell is relatively large in summer. Therefore, an environmentally friendly, one-component and excellent weather-resistant spray surface material is needed. Summary of the Invention

[0005] The object of the present invention is to overcome the above-mentioned defects existing in the prior art, and provide a one-component low-viscosity and high-weather-resistant spray surface material, which has the characteristics of environmental protection, low viscosity, excellent mechanical properties and high weather resistance. When applied to the runway spray surface layer, the construction is simple, the color is beautiful, and it is not easy to fade and lose color. The present invention also provides a preparation method thereof.

[0006] The one-component low-viscosity and high-weather-resistant spraying surface material described in the present invention comprises raw materials in the following parts by mass: polyether polyol: 50-60 parts, isocyanate: 10-15 parts, pigment: 2-4 parts, filler: 20-30 parts, dispersant: 1-1.5 parts, catalyst: 0.05-0.1 part, ultraviolet absorber: 0.5-1 part, antioxidant: 0.5-1 part.

[0007] The polyether polyol is prepared by mixing a polyether polyol with a weight-average molecular weight of 2000-4000 and a functionality of 2 and a polyether polyol with a weight-average molecular weight of 2000-6000 and a functionality of 3; the polyether polyol with a weight-average molecular weight of 2000-4000 and a functionality of 2 is preferably the polyether polyol INOVOL C240A produced by Shandong Yinuowei New Materials Co., Ltd.; the polyether polyol with a weight-average molecular weight of 2000-6000 and a functionality of 3 is preferably the polyether polyol EP3600 produced by Shandong Bluestar Dongda Co., Ltd.; the mass ratio of INOVOL C240A to EP3600 is 4:1.

[0008] The isocyanate is diphenylmethane diisocyanate, preferably MDI-50 of Wanhua Chemical Group Co., Ltd.

[0009] The pigment is a reactive pigment, and the reactive pigment is Red X64.

[0010] The dispersant is DISPERBYK-2164, produced by BYK Chemie GmbH.

[0011] The catalyst is an amine catalyst DMDLC, produced by Huntsman Corporation.

[0012] The ultraviolet absorber is ethyl 4-[[(methylphenylamino)methylene]amino]benzoate.

[0013] The antioxidant is n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

[0014] The filler is talc powder with a particle size of 800 mesh.

[0015] The preparation method of the one-component low-viscosity and high-weather-resistant spraying surface material comprises the following steps:

[0016] Put the polyether polyol and the dispersant into the reaction kettle, stir evenly, then add the pigment and the filler, stir evenly, heat up to 95 - 105 °C, and then carry out dehydration reaction under a vacuum of -0.1 MPa. After the reaction until the water content is <0.1 wt.%, cool down to 30 - 45 °C, then add the isocyanate, the ultraviolet absorber, and the antioxidant, heat up to 70 - 90 °C, and carry out prepolymerization reaction for 2 - 3 h. After the reaction ends, cool down to 40 - 50 °C, add the catalyst, and stir evenly to obtain a one-component low-viscosity and high-weather-resistant spray surface material.

[0017] The described one-component low-viscosity and high-weather-resistant spray surface material is used for spraying the runway surface layer. When the product is applied, add 1 times of EPDM particles and 20% of rubber powder to the one-component low-viscosity and high-weather-resistant spray surface material, mix evenly, and then spray it on the plastic base surface.

[0018] The present invention adopts the idea of one-component spray material, fundamentally eliminating the problems of inconsistent pigment addition amount and uneven site color caused by on-site mixed materials. Secondly, through reasonable formula design, the product has excellent strength. Abandoning the idea of adding conventional dispersed pigments, a new type of reactive pigment is introduced. Different from the color paste formed by ordinary pigments dispersed in polyol, this reactive pigment connects the pigment and the polyether component through graft reaction, and then makes the polymer chain containing reactive hydroxyl groups connect with the chromophore group, integrating the pigment and the polyether raw materials. During the polyurethane reaction process, the chromophore group is incorporated into the polymer network, achieving the excellent effects of firm color, no migration and no fading. Finally, a specific dispersant is introduced before the polyurethane reaction. The pigment is stabilized through steric hindrance, providing the same charge for different pigments. The repulsive force and steric hindrance obtained avoid co-flocculation and the floating color and blooming phenomena caused by pigments in the mixture, and further reduce the viscosity of the material, obtaining a uniform low-viscosity product.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0020] (1) The one-component low-viscosity and high-weather-resistant spray surface material of the present invention has good weather resistance. After long-term use, the product does not fade or lose color. Through reasonable formula design, a reactive pigment is introduced. The polymer containing reactive hydroxyl groups is connected with the chromophore group. During the polyurethane reaction process, the coloring group is incorporated into the polymer network, achieving the excellent effects of firm color, no migration and no fading. With the cooperation of the catalyst, the filler, and the dispersant, the compatibility between raw materials is ensured, the system color is uniform, and the mechanical properties of the product are excellent.

[0021] (2) The one-component low-viscosity and high-weather-resistant spraying surface material of the present invention has low material viscosity, and is convenient for construction at low temperatures. A dispersant is introduced before the polyurethane reaction. Through steric hindrance, the flocculation phenomenon is avoided, and the stability of pigments and fillers in the system is improved. The dispersant provides the same charge for different pigments and fillers, and reduces the viscosity of the material system through repulsive force and steric hindrance, resulting in a uniform low-viscosity product.

[0022] (3) The one-component low-viscosity and high-weather-resistant spraying surface material of the present invention adopts a one-component spraying surface material, which fundamentally avoids the problem of uneven site color caused by on-site mixing materials, and is applied to the spraying of the runway surface layer, with simple construction and convenient operation.

[0023] (4) The preparation method of the one-component low-viscosity and high-weather-resistant spraying surface material of the present invention has a simple process, and the raw materials are all environmentally friendly-oriented, ensuring the environmental protection of the product production and use processes. Specific Embodiments

[0024] The present invention will be further described below with reference to examples and comparative examples. The raw materials used in the examples are all commercially available conventional raw materials without special instructions; the process methods used in the examples are all conventional methods in the art without special instructions.

[0025] The raw materials used in the examples and comparative examples are described as follows:

[0026] INOVOL C240A: Shandong Yinuowei New Materials Co., Ltd.;

[0027] EP3600: Shandong Bluestar Dongda Co., Ltd.;

[0028] Red X64: Milliken Company, USA;

[0029] DISPERBYK-2164: BYK Chemie GmbH, Germany;

[0030] Amine catalyst DMDLC: Huntsman Corporation, USA.

[0031] The preparation method of the one-component low-viscosity and high-weather-resistant spraying surface material includes the following steps:

[0032] Add polyether polyol into a reaction kettle, add a dispersant, stir evenly, then add a reactive pigment and a filler, stir evenly, heat up to 95 - 105 °C, carry out dehydration reaction under a vacuum degree of -0.1 MPa, and end the reaction when the water content < 0.1 wt.%. Then cool down to 30 - 45 °C, add isocyanate, ultraviolet absorber, and antioxidant, heat up to 70 - 90 °C, and carry out prepolymerization reaction for 2 - 3 h. After the reaction ends, cool down to 40 - 50 °C, add a catalyst, and stir evenly to obtain a one-component low-viscosity and high-weather-resistant spraying surface material.

[0033] Example 1

[0034] The preparation method of the one-component low-viscosity and high-weather-resistant spraying surface material includes the following steps:

[0035] Add 400 kg of polyether polyol INOVOL C240A and 100 kg of polyether polyol EP3600 into a reaction kettle, add 15 kg of dispersant DISPERBYK-2164, stir evenly, then add 40 kg of reactive pigment Red X64 and 300 kg of filler 800-mesh talc powder, stir evenly, heat up to 95 °C, carry out dehydration reaction under a vacuum degree of -0.1 MPa, and end the reaction when the water content < 0.1 wt.%. Then cool down to 30 °C, add 124 kg of isocyanate MDI-50, 10 kg of ultraviolet absorber ethyl 4-[[(methylphenylamino)methylene]amino]benzoate, and 10 kg of antioxidant n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, heat up to 70 °C, carry out prepolymerization reaction for 3 h, cool down to 40 °C, add 1 kg of amine catalyst DMDLC, and stir evenly to obtain a one-component low-viscosity and high-weather-resistant spraying surface material.

[0036] Example 2

[0037] The preparation method of the one-component low-viscosity and high-weather-resistant spraying surface material includes the following steps:

[0038] Add 480 kg of polyether polyol INOVOL C240A and 120 kg of polyether polyol EP3600 into the reaction kettle, add 10 kg of dispersant DISPERBYK-2164, stir evenly, then add 20 kg of reactive pigment Red X64 and 259.5 kg of filler talc powder, stir evenly, heat up to 105 °C, and carry out dehydration reaction under a vacuum of -0.1 MPa. When the water content reaches <0.1 wt.%, the reaction ends. Then cool down to 45 °C, add 100 kg of isocyanate MDI-50, 5 kg of ultraviolet absorber ethyl 4-[[(methylphenylamino)methylene]amino]benzoate, and 5 kg of antioxidant n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, heat up to 90 °C, carry out prepolymerization reaction for 2 h, cool down to 50 °C, add 0.5 kg of amine catalyst DMDLC, stir evenly, and obtain a one-component low-viscosity and high-weather-resistant spraying surface material.

[0039] Example 3

[0040] The preparation method of the one-component low-viscosity and high-weather-resistant spraying surface material includes the following steps:

[0041] Add 472 kg of polyether polyol INOVOL C240A and 118 kg of polyether polyol EP3600 into the reaction kettle, add 11.2 kg of dispersant DISPERBYK-2164, stir evenly, then add 30 kg of reactive pigment Red X64 and 200 kg of filler 800-mesh talc powder, stir evenly, heat up to 100 °C, and carry out dehydration reaction under a vacuum of -0.1 MPa. When the water content reaches <0.1 wt.%, the reaction ends. Then cool down to 40 °C, add 150 kg of isocyanate MDI-50, 9 kg of ultraviolet absorber ethyl 4-[[(methylphenylamino)methylene]amino]benzoate, and 9 kg of antioxidant n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, heat up to 80 °C, carry out prepolymerization reaction for 2.5 h, cool down to 45 °C, add 0.8 kg of amine catalyst DMDLC, stir evenly, and obtain a one-component low-viscosity and high-weather-resistant spraying surface material.

[0042] Comparative Example 1

[0043] This comparative example is the same as Example 1, the difference is that conventional pigment iron oxide red with the same mass is used to replace the reactive pigment Red X64, and the other steps are the same as those in Example 1.

[0044] Comparative Example 2

[0045] This comparative example is the same as Example 1, the difference is that the dispersant DISPERBYK-2164 is replaced with DISPERBYK-110 with the same mass, and the other steps are the same as those in Example 1.

[0046] Comparative Example 3

[0047] The preparation method of the single-component low-viscosity and high-weather-resistant spraying surface material comprises the following steps:

[0048] Add 400 kg of polyether polyol INOVOL C240A and 100 kg of polyether polyol EP3600 into a reaction kettle, then add 40 kg of reactive pigment Red X64 and 300 kg of filler 800-mesh talc powder, stir evenly, heat up to 95 °C, carry out dehydration reaction under a vacuum degree of -0.1 MPa, and end the reaction when the water content is <0.1 wt.%. Then cool down to 30 °C, add 124 kg of isocyanate MDI-50, 10 kg of ultraviolet absorber ethyl 4-[[(methylphenylamino)methylene]amino]benzoate, and 10 kg of antioxidant octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, heat up to 70 °C, carry out prepolymerization reaction for 3 h, cool down to 40 °C, add 1 kg of amine catalyst DMDLC and 15 kg of dispersant DISPERBYK-2164, stir evenly, and obtain the single-component low-viscosity and high-weather-resistant spraying surface material.

[0049] Perform performance tests on the products prepared in Examples 1-3 and Comparative Examples 1-3. At the same time, prepare products according to the schemes described in Example 1 of Patent CN106118429A (recorded as Comparative Example 4) and Example 1 of Patent CN109651594A (recorded as Comparative Example 5), and perform performance tests on them with market conventional products. The performance test methods for the examples, comparative examples, and conventional products are exactly the same, and the test results are shown in Table 1.

[0050] Construct under the conditions of temperature 0-5 °C and 10-15 °C, and test the viscosity of the material; Aging conditions: Place the sample pieces at a temperature of 65 °C, a wavelength of 340 nm, and a light intensity of 0.51 W / m 2 Under the condition, first age for 108 min, then spray for 12 min, take this as a cycle, and repeat the treatment for 250 cycles and then conduct post-aging tests.

[0051] Table 1 Test Results

[0052]

[0053] As can be seen from Table 1, the products prepared by the present invention have excellent mechanical properties, high weather resistance, no fading or color bleeding after aging, and low construction viscosity, making them extremely easy to construct, compared with the products described in Comparative Example 4 and Comparative Example 5 and conventional market products; comparing Example 1 with Comparative Example 1, it can be seen that after replacing the ordinary dispersed pigment with a reactive pigment, the weather resistance of the product is significantly improved. By linking the reactive hydroxyl polymer chain to the chromophore group and incorporating the coloring group into the polymer network, the color fixation effect is achieved, that is, by introducing the reactive pigment into the product, excellent effects are produced; comparing Example 1 with Comparative Example 2, it can be seen that after changing the dispersant, the weather resistance of the product decreases and color bleeding occurs. The reason is that this reactive pigment has particularity, poor compatibility with the system, and the conventional dispersant cannot combine with this reactive pigment, making it difficult to fully exert the weather resistance effect of the reactive pigment; comparing Example 1 with Comparative Example 3, it can be seen that adding the dispersant in advance effectively reduces the interfacial tension between liquid-liquid and solid-liquid, improves the uniform dispersion of the pigment, greatly increases the loading amount of the pigment in the system, improves the hiding power and gloss of the system, and on the other hand, reduces the viscosity and enhances the fluidity of the system, making it more conducive to use at low temperatures.

Claims

1. A one-component, low-viscosity, high-weather-resistant spraying material, characterized in that: The invention comprises the following raw materials in parts by weight: polyether polyol: 50-60 parts, isocyanate: 10-15 parts, pigment: 2-4 parts, filler: 20-30 parts, dispersant: 1-1.5 parts, catalyst: 0.05-0.1 parts, ultraviolet absorber: 0.5-1 parts, antioxidant: 0.5-1 parts; The polyether polyol is a mixture of polyether polyol INOVOL C240A produced by Shandong Yinuowei New Materials Co., Ltd. and polyether polyol EP3600 produced by Shandong Bluestar Dongda Co., Ltd. in a mass ratio of 4:1; The pigment is a reactive pigment Red X64; The dispersant is DISPERBYK-2164; The method for preparing the one-component low-viscosity and high-weather-resistant spray-surface material comprises the following steps: Put polyether polyol and dispersant into the reaction kettle, stir evenly, then add pigment and filler, stir evenly, heat up to 95-105℃, then dehydrate under -0.1MPa vacuum, react until the moisture content is <0.1wt.%, cool down to 30-45℃, add isocyanate, ultraviolet absorber and antioxidant, heat up to 70-90℃, carry out prepolymerization for 2-3h, cool down to 40-50℃ after the reaction, add catalyst, stir evenly, and obtain a single-component low-viscosity and high weather-resistant spray material.

2. The one-component low-viscosity and high-weather-resistant spraying material according to claim 1, characterized in that: The isocyanate is diphenylmethane diisocyanate.

3. The one-component low-viscosity and high-weather-resistant spraying material according to claim 1, characterized in that: The catalyst is an amine catalyst DMDLC.

4. The one-component low-viscosity and high-weather-resistant spraying material according to claim 1, characterized in that: The ultraviolet absorber is ethyl 4-[[(methylphenylamino)methylene]amino]benzoate.

5. The one-component low-viscosity and high-weather-resistant spraying material according to claim 1, characterized in that: The antioxidant is n-octadecyl beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

6. The one-component low-viscosity and high-weather-resistant spraying material according to claim 1, characterized in that: The filler is talcum powder with a particle size of 800 meshes.

7. An application of the one-component low-viscosity high-weather-resistant spraying material according to any one of claims 1 to 6, characterized in that: Used for spraying of runway surface.

Images