High-performance polyurethane court material and preparation method thereof

Abstract

The present invention belongs to the technical field of polyurethane court materials, and specifically relates to a high-performance polyurethane court material and a preparation method thereof. The high-performance polyurethane court material described in the present invention is composed of component A and component B in a mass ratio of (4.5-5.5):1, and component A includes modified castor oil polyol, terminal amino polyether, chain extender, filler, pigment, anti-settling agent, water absorbent, dispersant, antioxidant, and ultraviolet absorber; component B includes isocyanate and polyether polyol. The high-performance polyurethane court material provided by the present invention solves the problems of conventional polyurethane courts being non-wear-resistant and having a low service life. The prepared product has excellent mechanical properties and good wear resistance, and the product cures quickly and has strong operability without the use of a catalyst. The preparation method of the present invention has a simple process and is easy to operate.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane court materials, and specifically relates to a high-performance polyurethane court material and a preparation method thereof. Background Art

[0002] In recent years, with the vigorous development of national fitness, the construction of sports venues and facilities has achieved remarkable results, among which polyurethane plastic sports venues have been widely used, especially in various communities, parks, schools, basketball courts, badminton courts, table tennis courts, etc. At present, in actual applications, many stadiums have problems such as wear, aging, and delamination due to their own strength and frequency of activities, which greatly reduces the service life of the venues, and requires multiple repairs and renovations in the future, increasing the maintenance cost.

[0003] At present, polyurethane court materials are divided into two-component and one-component. Two-component materials require additional catalysts to achieve curing. If the catalyst is forgotten or added too little during use, the material will not cure. The problem material is sticky and has poor strength, which makes it difficult to handle. Although one-component materials do not require catalysts, the thickness of a single coating is required to be less than 2mm. Multiple scrapings are required to reach the designed thickness, and the construction process is cumbersome.

[0004] CN110643015A discloses a highly wear-resistant and high-strength polyurethane court material, and a preparation method and a use method thereof. The material performance is improved by introducing modified carbon nanotubes, but the modified carbon nanotubes are prepolymerized in the isocyanate B component, and the preparation method does not have a dehydration step. In addition, the use of an organic bismuth catalyst has high catalytic activity, and its storage stability has problems.

[0005] Therefore, it is necessary to develop a two-component polyurethane court material with high strength, good wear resistance and no catalyst. Summary of the invention

[0006] The purpose of the present invention is to overcome the above-mentioned defects of the prior art, provide a high-performance polyurethane court material, solve the problems of conventional polyurethane courts being not wear-resistant and having a short service life, and the prepared product has excellent mechanical properties and good wear resistance, and the product cures quickly, has strong operability, and does not require the use of a catalyst; secondly, the present invention also provides a preparation method thereof, which has a simple process and is easy to operate.

[0007] The high-performance polyurethane court material of the present invention is composed of component A and component B in a mass ratio of (4.5-5.5):1, wherein component A includes the following raw materials in mass percentage: 20-25% modified castor oil polyol, 5-10% amino-terminated polyether, 0.5-0.7% chain extender, 60-65% filler, 1.5-3% pigment, 0.7-2% anti-settling agent, 2-3.5% water absorbent, 0.2-0.4% dispersant, 0.3-0.5% antioxidant, and 0.3-0.5% ultraviolet absorber;

[0008] Component B includes the following raw materials in percentage by mass: 70-80% isocyanate and 20-30% polyether polyol.

[0009] The modified castor oil polyol is an aromatic polyol with a number average molecular weight of 500-1200 and a functionality of 2-3.5, preferably SY798, purchased from Shanghai Shuyu Chemical Co., Ltd.

[0010] The polyether polyol is polyoxypropylene polyol with a number average molecular weight of 1000-3000 and a functionality of 2, preferably INOVOLC220, purchased from Shandong Yinuowei New Materials Co., Ltd.

[0011] The amino-terminated polyether is a primary amino-terminated polypropylene oxide compound, preferably LHD-1200, purchased from Shandong Longhua New Materials Co., Ltd.

[0012] The isocyanate is a mixture of polymeric MDI and diphenylmethane diisocyanate in a mass ratio of (1-2):1, the polymeric MDI is preferably PM-200, and the diphenylmethane diisocyanate is preferably MDI-50, and both PM-200 and MDI-50 are purchased from Yantai Wanhua Chemical Group Co., Ltd.

[0013] The chain extender is one of ethylene glycol and 1,4-butanediol. Ethylene glycol is purchased from Shandong Baihua Chemical Co., Ltd., and 1,4-butanediol is purchased from Wuhan Jixinyibang Biotechnology Co., Ltd.

[0014] The filler is heavy calcium carbonate with a mesh size of 400, purchased from Jiangxi Guangyuan Chemical Co., Ltd.

[0015] The pigment is iron oxide green, purchased from Shanghai Yipin Pigment Co., Ltd.

[0016] The anti-settling agent is precipitated silica, preferably ZB-3000, purchased from Jinan Zhongbei Fine Chemical Co., Ltd.

[0017] The water absorbent is 3A molecular sieve purchased from Pingxiang Liya New Materials Co., Ltd.

[0018] The dispersant is a nonionic neutral dispersant, preferably YRFC-03, purchased from Guangzhou Yourun Synthetic Materials Co., Ltd.

[0019] The antioxidant is a hindered phenol antioxidant, preferably Irganox 1135, purchased from BASF SE.

[0020] The ultraviolet absorber is a benzotriazole ultraviolet absorber, preferably Tinuvin 329, which is purchased from BASF.

[0021] The method for preparing the high-performance polyurethane court material comprises the following steps:

[0022] (1) Component A: Add modified castor oil polyol, amino-terminated polyether and chain extender into a reaction kettle, stir and heat to 60-70°C, then add filler, pigment, anti-settling agent, ultraviolet absorber and antioxidant, heat to 90-100°C, dehydrate for 2-3 hours under vacuum of -0.1MPa, then add water absorbent and dispersant, stir for 1-2 hours to obtain component A.

[0023] (2) Component B: Add isocyanate into the reaction kettle and stir evenly. Then add polyether polyol and heat to 80-85°C. Keep the temperature to react for 1-2 hours. After cooling, component B is obtained.

[0024] (3) When in use, mix components A and B according to the mass ratio and spread them on the field. After curing at room temperature, high-performance polyurethane court material is obtained.

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

[0026] (1) The high-performance polyurethane court material of the present invention, starting from the molecular structure design, introduces modified castor oil polyol, which has an aromatic structure and a long fatty chain structure of plant oils, reduces the polarity of the molecular chain, and gives the material better mechanical properties; on the other hand, by combining with terminal amino polyether to introduce primary amino groups, and cooperate with small molecule chain extenders, the curing speed of the material is greatly improved, the self-catalytic characteristics of the material are realized, and the effect of curing at room temperature is achieved without adding a catalyst, which improves the construction efficiency, and the prepared product has high hardness and good wear resistance.

[0027] (2) The high-performance polyurethane court material of the present invention, while introducing modified castor oil polyol, terminal amino polyether and chain extender, effectively reduces the viscosity of the liquid through the reasonable compounding of isocyanate in component B, synergistically using low oil absorption filler and non-ionic neutral dispersant, so that the material maintains high activity and high strength while having good operational leveling properties, reducing the difficulty of construction.

[0028] (3) The preparation method of the high-performance polyurethane court material of the present invention has a simple process, can be cured without a catalyst when used, is easy to operate, and is suitable for industrial production. DETAILED DESCRIPTION

[0029] The present invention is further described below with reference to the embodiments, but they do not limit the implementation of the present invention.

[0030] The raw materials used in the examples and comparative examples are conventional commercially available raw materials unless otherwise specified, and the process methods used in the examples and comparative examples are conventional methods in the art unless otherwise specified.

[0031] Some of the raw materials used in the examples and comparative examples are described as follows:

[0032] SY798: Shanghai Shuyu Chemical Co., Ltd.;

[0033] LHD-1200: Shandong Longhua New Materials Co., Ltd.

[0034] PM-200: Yantai Wanhua Chemical Group Co., Ltd.;

[0035] MDI-50: Yantai Wanhua Chemical Group Co., Ltd.

[0036] INOVOLC220: Shandong Yinuowei New Materials Co., Ltd.;

[0037] Ethylene glycol: Shandong Baihua Chemical Co., Ltd.;

[0038] 1,4-Butanediol: Wuhan Jixinyibang Biotechnology Co., Ltd.;

[0039] Heavy calcium carbonate: Jiangxi Guangyuan Chemical Co., Ltd.;

[0040] Iron oxide green: Shanghai Yipin Pigment Co., Ltd.;

[0041] ZB-3000: Jinan Zhongbei Fine Chemical Co., Ltd.

[0042] 3A molecular sieve: Pingxiang Liya New Materials Co., Ltd.;

[0043] YRFC-03: Guangzhou Yourun Synthetic Materials Co., Ltd.;

[0044] Irganox 1135: BASF SE;

[0045] Tinuvin 329: BASF SE;

[0046] Castor oil: Jinan Haiyuan Chemical Co., Ltd.

[0047] The high-performance polyurethane court material of the present invention is composed of component A and component B in a mass ratio of (4.5-5.5):1, wherein component A includes the following raw materials in mass percentage: 20-25% modified castor oil polyol, 5-10% amino-terminated polyether, 0.5-0.7% chain extender, 60-65% filler, 1.5-3% pigment, 0.7-2% anti-settling agent, 2-3.5% water absorbent, 0.2-0.4% dispersant, 0.3-0.5% antioxidant, and 0.3-0.5% ultraviolet absorber;

[0048] Component B includes the following raw materials in percentage by mass: 70-80% isocyanate and 20-30% polyether polyol.

[0049] The method for preparing the high-performance polyurethane court material comprises the following steps:

[0050] (1) Component A: Add modified castor oil polyol, amino-terminated polyether and chain extender into a reaction kettle, stir and heat to 60-70°C, then add filler, pigment, anti-settling agent, ultraviolet absorber and antioxidant, heat to 90-100°C, dehydrate for 2-3 hours under vacuum of -0.1MPa, then add water absorbent and dispersant, stir for 1-2 hours to obtain component A.

[0051] (2) Component B: Add isocyanate into the reaction kettle and stir evenly. Then add polyether polyol and heat to 80-85℃. Keep the temperature to react for 1-2h. Then cool to 60℃ and discharge the mixture to obtain component B.

[0052] (3) When in use, mix components A and B according to the mass ratio and spread them on the field. After curing at room temperature, high-performance polyurethane court material is obtained.

[0053] Example 1

[0054] The high-performance polyurethane court material is composed of component A and component B in a mass ratio of 5:1, wherein component A includes the following raw materials in mass percentage: 20% SY798, 10% LHD-1200, 0.5% ethylene glycol, 60% heavy calcium carbonate, 3% iron oxide green, 2% ZB-3000, 3.5% 3A molecular sieve, 0.2% YRFC-03, 0.5% Irganox 1135, 0.3% Tinuvin 329;

[0055] Component B includes the following raw materials in percentage by mass: 70% isocyanate (PM-200:MDI-50=1:1), 30% INOVOLC220.

[0056] The method for preparing the high-performance polyurethane court material comprises the following steps:

[0057] (1) Component A: SY798, LHD-1200 and ethylene glycol were added to a kettle, stirred and heated to 60°C, then heavy calcium carbonate, iron oxide green, ZB-3000, Tinuvin 329 and Irganox 1135 were added, the temperature was raised to 100°C, and dehydrated for 2 hours under a vacuum of -0.1 MPa, then 3A molecular sieve and YRFC-03 were added, and stirred for 1 hour to obtain component A.

[0058] (2) Component B: Add PM-200 and MDI-50 in a mass ratio of 1:1 into a reactor, stir evenly, then add INOVOLC220, heat to 85°C, keep the temperature for 2 hours, cool to 60°C and discharge to obtain component B.

[0059] (3) When in use, mix components A and B in a mass ratio of 5:1 and spread them on the field. After curing at room temperature, high-performance polyurethane court material is obtained.

[0060] Example 2

[0061] The high-performance polyurethane court material is composed of component A and component B in a mass ratio of 4.5:1, wherein component A includes the following raw materials in mass percentage: 25% SY798, 5% LHD-1200, 0.7% ethylene glycol, 62% heavy calcium carbonate, 2% iron oxide green, 1.2% ZB-3000, 3% 3A molecular sieve, 0.3% YRFC-03, 0.4% Irganox 1135, 0.4% Tinuvin 329;

[0062] Component B includes the following raw materials in percentage by mass: 80% isocyanate (PM-200:MDI-50=2:1), 20% INOVOLC220.

[0063] The preparation method of the high-performance polyurethane court material comprises the following steps:

[0064] (1) Component A: SY798, LHD-1200 and ethylene glycol were added to a kettle, stirred and heated to 70°C, then heavy calcium carbonate, iron oxide green, ZB-3000, Tinuvin 329 and Irganox 1135 were added, the temperature was raised to 90°C, and dehydrated for 3 hours under vacuum at -0.1 MPa, then 3A molecular sieve and YRFC-03 were added, and stirred for 1.5 hours to obtain component A.

[0065] (2) Component B: Add PM-200 and MDI-50 in a mass ratio of 2:1 into a reactor, stir evenly, then add INOVOLC220, heat to 80°C, keep the temperature for 1 hour, cool to 60°C and discharge to obtain component B.

[0066] (3) When in use, mix components A and B in a mass ratio of 4.5:1 and spread them on the field. After curing at room temperature, high-performance polyurethane court material is obtained.

[0067] Example 3

[0068] The high-performance polyurethane court material is composed of component A and component B in a mass ratio of 5.5:1, wherein component A includes the following raw materials in mass percentage: 22% SY798, 7% LHD-1200, 0.6% 1,4-butanediol, 65% heavy calcium carbonate, 1.5% iron oxide green, 0.7% ZB-3000, 2% 3A molecular sieve, 0.4% YRFC-03, 0.3% Irganox 1135, 0.5% Tinuvin329;

[0069] Component B includes the following raw materials in percentage by mass: 75% isocyanate (PM-200:MDI-50=1.5:1), 25% INOVOLC220.

[0070] The method for preparing the high-performance polyurethane court material comprises the following steps:

[0071] (1) Component A: SY798, LHD-1200 and 1,4-butanediol were added into a kettle, stirred and heated to 65°C, then heavy calcium carbonate, iron oxide green, ZB-3000, Tinuvin 329 and Irganox 1135 were added, the temperature was raised to 95°C, and dehydrated for 2.5 hours under vacuum of -0.1 MPa, then 3A molecular sieve and YRFC-03 were added, and stirred for 1 hour to obtain component A.

[0072] (2) Component B: Add PM-200 and MDI-50 in a mass ratio of 1.5:1 into a reactor, stir evenly, then add INOVOLC220, raise the temperature to 83°C, keep the temperature for 1.5 hours, cool to 60°C and discharge the material to obtain component B.

[0073] (3) When in use, mix components A and B in a mass ratio of 5.5:1 and spread them on the field. After curing at room temperature, high-performance polyurethane court material is obtained.

[0074] Comparative Example 1

[0075] This comparative example is the same as Example 1, except that SY798 in component A is replaced by castor oil. In comparative example 1, component A includes the following raw materials in percentage by mass: 24% castor oil, 10% LHD-1200, 0.5% ethylene glycol, 56% heavy calcium carbonate, 3% iron oxide green, 2% ZB-3000, 3.5% 3A molecular sieve, 0.2% YRFC-03, 0.5% Irganox 1135, and 0.3% Tinuvin329; the raw materials of component B and their percentage by mass, and the preparation method of the high-performance polyurethane court material are the same as those in Example 1.

[0076] Comparative Example 2

[0077] This comparative example is the same as Example 1, except that the amino-terminated polyether LHD-1200 in component A is replaced by INOVOL C220 of equal mass percentage, and component A in comparative example 2 comprises the following raw materials in mass percentage: 20% SY798, 10% INOVOLC220, 0.5% ethylene glycol, 60% heavy calcium carbonate, 3% iron oxide green, 2% ZB-3000, 3.5% 3A molecular sieve, 0.2% YRFC-03, 0.5% Irganox 1135, 0.3% Tinuvin 329; the raw materials of component B and their mass percentages, and the preparation method of the high-performance polyurethane court material are the same as those in Example 1.

[0078] Comparative Example 3

[0079] This comparative example is the same as Example 1, except that SY798 in component A is replaced by castor oil and the amino-terminated polyether LHD-1200 is removed. In comparative example 3, component A includes the following raw materials in percentage by mass: 24% castor oil, 10% INOVOLC220, 0.5% ethylene glycol, 56% heavy calcium carbonate, 3% iron oxide green, 2% ZB-3000, 3.5% 3A molecular sieve, 0.2% YRFC-03, 0.5% Irganox 1135, and 0.3% Tinuvin 329; the raw materials of component B and their percentage by mass, and the preparation method of the high-performance polyurethane court material are the same as those in Example 1.

[0080] Comparative Example 4

[0081] This comparative example is the same as Example 1, except that the isocyanate (PM-200:MDI-50=1:1) mixture in component B is replaced with PM-200 of the same mass percentage, and the remaining raw material proportions and preparation methods are the same as those in Example 1.

[0082] Comparative Example 5

[0083] The difference from Example 1 is that the process of adding the water absorbent 3A molecular sieve in the preparation method is different.

[0084] The raw material compositions and mass percentages of component A and component B are the same as those in Example 1.

[0085] The method for preparing the high-performance polyurethane court material comprises the following steps:

[0086] (1) Component A: SY798, LHD-1200 and ethylene glycol were added into a reactor, stirred and heated to 60°C, and then heavy calcium carbonate, 3A molecular sieve, iron oxide green, ZB-3000, Tinuvin 329 and Irganox 1135 were added. The temperature was raised to 100°C, and dehydrated for 2 hours under a vacuum of -0.1 MPa. Then YRFC-03 was added and stirred for 1 hour to obtain component A.

[0087] (2) Component B: Add PM-200 and MDI-50 in a mass ratio of 1:1 into a reactor, stir evenly, then add INOVOLC220, heat to 85°C, keep the temperature for 2 hours, cool to 60°C and discharge to obtain component B.

[0088] (3) When in use, mix components A and B in a mass ratio of 5:1 and spread them on the field. After curing at room temperature, high-performance polyurethane court material is obtained.

[0089] The polyurethane court materials prepared in Examples 1-3 and Comparative Examples 1-5 were subjected to performance tests. The operable time was tested in accordance with GB / T7123.1-2015, the tensile strength and elongation at break were tested in accordance with GB / T528-2009, the hardness was tested in accordance with GB / T2411-2008, and the wear resistance was tested in accordance with GB / T1768-2006 (test conditions: rubber grinding wheel model CS-10F, load 500g, number of revolutions 1000r). The test results are shown in Table 1.

[0090] Table 1 Test results

[0091]

[0092] As can be seen from Table 1, compared with the comparative examples, the high-performance polyurethane court materials prepared in Examples 1-3 have obvious product performance advantages. The mechanical properties and wear resistance of the polyurethane court material prepared in Comparative Example 1 are reduced, because the castor oil molecular chain segment has no aromatic structure, resulting in reduced product activity, poor mechanical properties and wear resistance; after replacing the amino-terminated polyether in Comparative Example 2, the activity intensity is also reduced accordingly; the polyurethane court material prepared in Comparative Example 3 has a long operation time and the worst performance, because castor oil and polyether polyol are used, and the product activity is low without a catalyst, and self-catalysis cannot be achieved, and the curing is slow, resulting in poor product cross-linking strength, which cannot meet the site use requirements; Comparative Example 4 replaces the isocyanate from a mixture with a single substance PM-200, and the product activity becomes higher, resulting in a shorter operation time, and it is impossible to spread and construct on site; Comparative Example 5 adjusts the process to change the order of adding the water absorbent 3A molecular sieve, and the mechanical properties of the product are significantly reduced, because the water absorbent is added before dehydration, absorbs a large amount of water, reduces its own water absorption performance, causes the product to foam, and reduces physical properties. The comparison of comparative examples 1-5 shows that the introduction of modified castor oil polyol, amino-terminated polyether and chain extender, together with the reasonable compounding of isocyanate in component B, the synergistic effect of low oil absorption filler and non-ionic neutral dispersant and water absorbent, effectively improves the operational leveling, achieves self-catalysis without a catalyst, and the prepared product has excellent mechanical properties, good wear resistance, strong operability and fast curing time.

Claims

1. A high-performance polyurethane court material, characterized in that: The invention is composed of component A and component B in a mass ratio of (4.5-5.5):1, wherein component A comprises the following raw materials in mass percentage: 20-25% modified castor oil polyol, 5-10% amino-terminated polyether, 0.5-0.7% chain extender, 60-65% filler, 1.5-3% pigment, 0.7-2% anti-settling agent, 2-3.5% water absorbent, 0.2-0.4% dispersant, 0.3-0.5% antioxidant, and 0.3-0.5% ultraviolet absorber; Component B includes the following raw materials in percentage by mass: 70-80% isocyanate, 20-30% polyether polyol; The modified castor oil polyol is SY798, purchased from Shanghai Shuyu Chemical Co., Ltd. The amino-terminated polyether is a primary amino-terminated polypropylene oxide compound; The isocyanate is a mixture of polymeric MDI and diphenylmethane diisocyanate; The preparation method of the component A is as follows: modified castor oil polyol, terminal amino polyether and chain extender are put into a reaction kettle, stirred and heated to 60-70°C, then fillers, pigments, anti-settling agents, ultraviolet absorbers and antioxidants are added, the temperature is raised to 90-100°C, dehydrated for 2-3 hours under a vacuum condition of -0.1MPa, and then a water absorbent and a dispersant are added, and stirred for 1-2 hours to obtain the obtained component.

2. The high-performance polyurethane court material according to claim 1, characterized in that: The polyether polyol is polyoxypropylene polyol with a number average molecular weight of 1000-3000 and a functionality of 2.

3. The high performance polyurethane court material according to claim 1, characterized in that: The chain extender is one of ethylene glycol and 1,4-butanediol.

4. The high performance polyurethane court material according to claim 1, characterized in that: The filler is heavy calcium carbonate and the pigment is iron oxide green.

5. The high performance polyurethane court material according to claim 1, characterized in that: The anti-settling agent is precipitated silica, and the water absorbent is 3A molecular sieve.

6. The high performance polyurethane court material according to claim 1, characterized in that: The dispersant is a nonionic neutral dispersant.

7. The high performance polyurethane court material according to claim 1, characterized in that: The antioxidant is a hindered phenol antioxidant.

8. The high performance polyurethane court material according to claim 1, characterized in that: The ultraviolet absorber is a benzotriazole ultraviolet absorber.

9. The high performance polyurethane court material according to claim 1, characterized in that: The isocyanate is a mixture of polymeric MDI and diphenylmethane diisocyanate, and the mass ratio of the two is (1-2):

1.

10. A method for preparing the high-performance polyurethane court material according to any one of claims 1 to 9, characterized in that: The following steps are involved: (1) Component A: Add modified castor oil polyol, amino-terminated polyether and chain extender into a reaction kettle, stir and heat to 60-70°C, then add filler, pigment, anti-settling agent, ultraviolet absorber and antioxidant, heat to 90-100°C, dehydrate for 2-3 hours under vacuum degree of -0.1MPa, then add water absorbent and dispersant, stir for 1-2 hours, and obtain component A; (2) Component B: Add isocyanate into a reaction kettle and stir evenly, then add polyether polyol, raise the temperature to 80-85°C, keep the temperature for reaction for 1-2 hours, and then cool down to obtain component B; (3) When in use, mix components A and B according to the mass ratio and spread them on the field. After curing at room temperature, high-performance polyurethane court material is obtained.

Images