A polyurethane plastic track adhesive with reactive thixotropy and long operating time, as well as its preparation method and application

Abstract

The present invention relates to a polyurethane plastic track adhesive with a long operating time and reactive thixotropy, as well as a preparation method and application thereof. The adhesive comprises a component A polyurethane prepolymer and a component B polyether composite material. In the component B, the polyether polyol comprises at least one polyether polyol with a functionality of 3 and a molecular weight of less than 1000 g / mol. The adhesive of the present invention is prepared by reacting isocyanate with a multifunctional small molecule polyether polyol and cooperating with a carboxylate block polymer dispersant. It does not contain solvents or thixotropic agents, is environmentally friendly and non-toxic, and has reactive thixotropy. It has a long operating time and can effectively solve the flow problem of the plastic track surface construction, making it convenient for on-site construction. In addition, the characteristics of reactive thixotropy and the use of special dispersants provide it with sufficient operating time to prevent the spraying equipment from "blocking the pipe", while also effectively suppressing the escape of glue and ensuring that the glue and EPDM particles are fully wrapped.

Description

Technical Field

[0001] The present invention relates to the field of polyurethane adhesives, and in particular to the development of an environmentally friendly polyurethane adhesive with a reactive thixotropic property and a long operating time, and its application in plastic track sports surface materials. Background Art

[0002] Plastic tracks are different from traditional asphalt and cement tracks. Plastic tracks made with polyurethane adhesives have the characteristics of high elasticity, excellent weather resistance and high strength. They are also easy to construct and can be widely used in campus sports fields, park fitness trails, competition venues and other fields.

[0003] Among them, the two-component polyurethane adhesive mainly includes components containing isocyanate groups and hydroxyl groups. After mixing with EPDM particles, the adhesive is reacted and applied, and can be used as the surface material of plastic tracks. However, while the lower viscosity provides it with excellent leveling properties, it also brings the problem of excessive flow during construction, especially when the spraying is too thick at one time, the glue will sink to the bottom or flow to the surroundings, resulting in the phenomenon of "leaking" of particles. Although the problem can be slightly alleviated by repeated spraying or mixing the two components with particles and placing them for a period of time, and then applying the adhesive after the viscosity increases, it still cannot effectively solve the problem. At the same time, the increase in viscosity will shorten the operating time of the product construction, bring the risk of "pipe blocking" to the spraying equipment, and bring inconvenience to the construction. Therefore, there is an urgent need to develop a polyurethane adhesive with a reactive thixotropic property and a long operating time to solve the above problems.

[0004] CN 104559734 A discloses a two-component chemical reaction thixotropic polyurethane waterproof coating and its preparation method. It features a reaction between an amine reactant and an isocyanate, generating a polyurea compound containing a large number of urea groups under the action of a specific polymerization inhibitor. This polyurea compound then forms numerous hydrogen bonds with the polyurethane, dramatically increasing the static viscosity of the system and achieving excellent thixotropy. However, the amine reactant primarily uses MOCA, which has excessively high reactivity due to its terminal amino groups. This results in a limited operating time of 5-10 minutes after mixing the two components, making it difficult to apply. Furthermore, MOCA, a carcinogen clearly identified by the World Health Organization's International Agency for Research on Cancer in 2012, poses significant risks to the human body.

[0005] CN 103189410 A discloses a method for preparing a two-component polyurethane adhesive with a thixotropic effect. Component A contains 0.1 to 10 weight percent of a sterically hindered amine with a primary amino group. After mixing and reacting with an isocyanate, the adhesive maintains a low viscosity. Furthermore, the sterically hindered amine with the primary amino group provides a thixotropic effect, preventing free flow without external pressure. Although Henkel limits the molecular weight of the polyol components to above 500 g / mol and the molecular weight of the isocyanate to below 1000 g / mol to reduce reactivity, the adhesive still has an open time of only 60 seconds, making it unsuitable for use in the plastic track industry. Furthermore, the odor and toxicity of the aromatic primary amines also limit the adhesive's application in many fields.

[0006] CN 105602514 A discloses a two-component, highly thixotropic polyurethane adhesive. This adhesive achieves high thixotropy through the synergistic effect of surfactants and fumed silica, combined with a stoichiometric filler. The adhesive can be applied to vertical or vertical surfaces and is used for bonding structural components in refrigerated trucks and truck bodies. However, the low specific gravity of fumed silica makes it highly volatile in the air, which can present certain production challenges.

[0007] CN 111748310 A discloses a two-component polyurethane adhesive and its preparation method. The adhesive features a large amount of thixotropic filler, such as nano-calcium carbonate, added to maintain mechanical properties, enhance thixotropy, and reduce costs. The adhesive can be used in automotive windshield adhesives, ensuring effective connection between the windshield and the vehicle body. However, the use of nano-calcium carbonate also makes the adhesive difficult to manufacture, and its curing speed of 3 mm / 24 hours precludes its application in the field of plastic tracks.

[0008] In summary, existing research on the thixotropy of polyurethane adhesives primarily focuses on the addition of thixotropic agents or fillers and the selection of suitable amine reactants. These studies fail to fully address the requirements for the use of synthetic materials in plastic track surfaces. These surfaces place high demands on polyurethane adhesives, requiring sufficient operating time, complete curing within 24 hours, no exposed particles, compliance with national environmental standards, and sufficient strength after curing. Failure to meet any of these requirements renders the adhesive unsuitable for use in plastic track surfaces. Summary of the Invention

[0009] In response to the above-mentioned problems existing in the prior art, the present invention provides a polyurethane plastic track adhesive with a long operating time and reactive thixotropy. The adhesive is prepared by reacting an isocyanate with a multifunctional small molecule polyether polyol in conjunction with a carboxylate block polymer dispersant. The adhesive is solvent-free and thixotropic, environmentally friendly and non-toxic, and exhibits reactive thixotropy. It has a long operating time and can effectively solve the problem of flow during plastic track surface construction, facilitating on-site construction. Furthermore, the reactive thixotropy and the use of a special dispersant provide ample operating time to prevent "pipe clogging" in the spraying equipment while effectively suppressing the escape of glue and ensuring sufficient encapsulation of the glue and EPDM particles.

[0010] Specifically, the present invention achieves the above-mentioned purpose through the following technical solutions:

[0011] The present invention provides a polyurethane plastic track adhesive with reactive thixotropy, comprising a component A of a polyurethane prepolymer and a component B of a polyether composite material, wherein the mass ratio of the component A to the component B is 0.5 to 2:1, preferably 0.5 to 1:1;

[0012] The polyurethane prepolymer of component A comprises the following components by weight:

[0013]

[0014]

[0015] The polyether composition of component B comprises the following components by weight:

[0016]

[0017] In component B, the polyether polyol comprises at least one polyether polyol having a functionality of 3 and a molecular weight of less than 1000 g / mol, preferably 400-700 g / mol; its mass proportion is 2-15%, preferably 5-10%, based on the total mass of the polyether polyol in component B being 100%.

[0018] In the present invention, the isocyanate content NCO% in the A component is 4 to 20 wt%, preferably 6 to 12 wt%;

[0019] In the present invention, the hydroxyl value of the B component is 50 to 130 mgKOH / g, preferably 60 to 80 mgKOH / g.

[0020] In the polyurethane prepolymer of component A of the present invention, the isocyanate is selected from one or more of 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate, preferably one or more of WANOL MDI-50FB, WANOL MDI-100F, WANOL PM200 and the like.

[0021] In the polyurethane prepolymer of component A of the present invention, the polyether polyol is selected from one or more of a polyether polyol having a molecular weight of 1000 to 5000 g / mol, a functionality of 2, and a hydroxyl value of 20 to 120 mgKOH / g and a polyether polyol having a molecular weight of 3000 to 6000 g / mol, a functionality of 3, and a hydroxyl value of 25 to 60 mgKOH / g, preferably one or more of polyethylene oxide unsaturated polyols and polypropylene oxide unsaturated polyols, such as one or more of WANOL DL-1000D, WANOL DL-2000, WANOL DL-4000D, WANOL 2130, WANOL 2140F, WANOL F3128, WANOL F3135, and WANOL F3156.

[0022] In the polyurethane prepolymer of component A of the present invention, the plasticizer is selected from one or more of C17-C24 long-chain chlorinated paraffin, chloropalm oil methyl ester, dioctyl terephthalate and acetyl tributyl citrate, preferably acetyl tributyl citrate, such as acetyl tributyl citrate (ATBC) of Shandong Kexing.

[0023] In the polyurethane prepolymer of component A of the present invention, the ultraviolet absorber is selected from a high-efficiency ultraviolet absorber of the benzotriazole type that can absorb ultraviolet rays with a wavelength of 270 to 340 nm, preferably one or more of UV-P, UV-1, and C81, such as UV-P of Changzhou Xin Ce Polymer Materials.

[0024] In the polyether composition of component B of the present invention, the polyether polyol comprises at least one polyether polyol having a functionality of 3 and a molecular weight of less than 1000 g / mol, preferably 400 to 700 g / mol; preferably, polyoxypropylene triol having a functionality of 3, a molecular weight of 400 g / mol, and a hydroxyl value of 420 mgKOH / g, such as WANOL R-2304;

[0025] Furthermore, the polyether polyol further comprises one or more of other polyether polyols having a molecular weight of 1000-5000 g / mol, a functionality of 2, a hydroxyl value of 20-120 mgKOH / g and a molecular weight of 3000-6000 g / mol, a functionality of 3, and a hydroxyl value of 25-60 mgKOH / g. Preferably, the other polyether polyol further comprises a conventional polyether chain-extended with PO or end-capped with PO chain-extended with EO, more preferably one or more of polyethylene oxide unsaturated polyols and polypropylene oxide unsaturated polyols, such as WANOL DL-1000D, WANOL DL-2000, WANOL DL-4000D, WANOL 2130, WANOL 2140F, WANOL F3128, WANOL F3135, WANOL F3156, etc.

[0026] In the polyether composition of component B of the present invention, the chain extender is selected from one or more of a polyurethane chain extender, diethylene glycol and triethanolamine, preferably WANOL 1104.

[0027] In the polyether composition of component B of the present invention, the filler is one or more of heavy calcium carbonate with a mesh size of 400-1000, preferably 400-800, talc with a mesh size of 400-1000, preferably 600-800, and light calcium carbonate with a mesh size of 400-1250, preferably 800-1250.

[0028] In the polyether composition of component B of the present invention, the pigment is selected from iron oxide red, iron oxide green or phthalocyanine blue.

[0029] In the polyether composition of component B of the present invention, the plasticizer is one or more of C17-C24 long-chain chlorinated paraffin, chloropalm oil methyl ester, dioctyl terephthalate and acetyl tributyl citrate, preferably acetyl tributyl citrate, such as acetyl tributyl citrate (ATBC) from Shandong Kexing.

[0030] In the polyether composition of component B of the present invention, the acidic polymer dispersant is a carboxylate block polymer having a viscosity greater than 1000 cps, preferably 2000-5000 cps, and an acid value of 50-200 mgKOG / g, preferably 50-80 mgKOG / g; and is selected from one or more of carboxylate block copolymers and polyacid ester block copolymers, such as Silok-7456F, Silok-7455H, etc.

[0031] In the polyether composition of component B of the present invention, the catalyst is selected from one or more of dibutyltin dilaurate, didodecylthiodibutyltin, bismuth neodecanoate, bismuth isooctanoate, zinc neodecanoate and zinc isooctanoate.

[0032] The present invention also provides a method for preparing the above-mentioned reactive thixotropic polyurethane adhesive, comprising the following steps:

[0033] 1) Preparation of component A polyurethane prepolymer:

[0034] Mix isocyanate and polyether polyol, react at 80-100°C, preferably 80-85°C for 2-3 hours until NCO approaches the theoretical value, then stop the reaction, cool to 50-60°C, add plasticizer and UV absorber, stir for 20-30 minutes to mix evenly, discharge and seal with nitrogen for storage;

[0035] 2) Preparation of component B polyether combination material:

[0036] Mix the polyether polyol and pigment, stir for 0.5 to 1 hour to make the mixture uniform, heat to 100 to 120°C, add filler, plasticizer and acidic polymer dispersant, grind and stir for 0.5 to 1 hour, vacuum dehydrate for 2 to 3 hours to reduce the water content to below 100 ppm, cool to 40 to 50°C, then add chain extender and catalyst, stir evenly and seal for storage.

[0037] The present invention further provides the use of the reactive thixotropic polyurethane adhesive in plastic track sports surface materials.

[0038] The present invention provides a plastic track surface material, which is prepared by mixing the above-mentioned reactive thixotropic polyurethane adhesive and EPDM (ethylene propylene diene monomer) particles in a mass ratio of 1:0.5 to 2, preferably 1:1 to 1.5, for example 1:1;

[0039] In the present invention, the EPDM particles have a particle size of 1 to 4 mm, preferably 1 to 3 mm, and are selected from the Mele rubber particles produced by Guangdong Chuanao High-tech Technology Co., Ltd.

[0040] The method for preparing the plastic track surface material of the present invention comprises the following steps:

[0041] Mix the polyurethane prepolymer (component A) and the polyether component (component B) of the reactive thixotropic polyurethane adhesive for 1 to 2 minutes, then mix and stir evenly with the EPDM particles, and spray on the elastic base of the plastic track within 10 minutes to form a surface layer.

[0042] Preferably, the surface layer has a thickness of 2 to 3 mm.

[0043] The plastic track surface material of the present invention has a thixotropic index of more than 4, an operating time of 20 to 25 minutes, and a room temperature curing time of less than 24 hours.

[0044] The adhesive of the present invention does not require the use of any aromatic amines and thixotropic agents. Through the reaction of the trifunctional small molecule polyether polyol contained in the polyether polyol in component B with isocyanate, it can cross-link within 10 minutes to form a cage-like structure, wrapping the filler, thereby sharply increasing the static viscosity of the system to form a paste, producing a thixotropic effect, and promoting the full wrapping of the glue and EPDM particles. It can effectively solve the problem of flow during the construction of the plastic track surface layer. At the same time, the long operation time of 20 to 25 minutes can effectively prevent the spraying equipment from "blocking the pipe".

[0045] Among them, polyether polyols with a functionality of 3 and a molecular weight of less than 1000 g / mol contain three hydroxyl groups per molecule. Initially, they can react rapidly with three isocyanate-containing prepolymer molecules, forming a cross-linked network. As the reaction proceeds, the molecules within the system continue to move, and some fillers become entangled with this network, ultimately forming a cage-like structure and producing a thixotropic effect. This is a feature that large molecular weight or low-functionality polyether polyols lack. Large molecular weight polyether polyols have long chain segments and low initial activity, making it difficult to quickly crosslink and form a network structure. Low-functionality polyether polyols, on the other hand, contain only two active reactive groups and cannot crosslink to form a network structure, making it difficult to produce the thixotropic effect mentioned in this invention.

[0046] Furthermore, the acidic polymer dispersant introduced in this invention promotes uniform dispersion of the polyether composition while effectively suppressing the system's reactivity, allowing for a longer operating time in the early stages of the reaction. Unlike small-molecule acids, this acidic dispersant is composed of long-chain polymer segments. As the polyurethane chain continues to expand over time, the acidic effect on its reactivity decreases, ensuring complete curing within 24 hours.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] (1) The two-component polyurethane adhesive provided by the present invention has good reactive thixotropy, which can effectively solve the flow problem faced by the construction of the plastic track surface layer and ensure that the glue and EPDM particles are fully wrapped;

[0049] (2) The two-component polyurethane adhesive provided by the present invention does not use any aromatic amines and thixotropic agents (nano calcium carbonate, bentonite, silica, etc.), and is more environmentally friendly and has a wider range of applications than traditional polyurethane adhesives;

[0050] (3) The two-component polyurethane adhesive provided by the present invention does not use any amine chain extender, and the acidic dispersant can effectively inhibit the activity of the adhesive. The synergistic effect makes the early reaction relatively mild, and can provide a longer operation time of 20-25 minutes, effectively avoiding the risk of "pipe blocking" of the spraying equipment. Specific implementation plan

[0051] The present invention will be further described below with reference to the following embodiments. However, the present invention is not limited to the listed embodiments and also includes any other known changes within the scope of the claimed invention.

[0052] In the examples and comparative examples of the present invention, the sources of the main raw materials are as follows. Unless otherwise specified, other raw materials and reagents were purchased from common commercial sources:

[0053] 2,4-Diphenylmethane diisocyanate: Wanhua Chemical Group Co., Ltd., WANOL MDI-50FB;

[0054] 4,4-Diphenylmethane diisocyanate: Wanhua Chemical Group Co., Ltd., WANOL MDI-100F;

[0055] Polymethylene polyphenyl isocyanate: Wanhua Chemical Group Co., Ltd., WANOL PM200;

[0056] Polyether diol: Wanhua Chemical Group Co., Ltd., WANOL DL-1000D, WANOL DL-2000, WANOL DL-4000D;

[0057] Polyether triol: Wanhua Chemical Group Co., Ltd., WANOL F3135;

[0058] Polyoxypropylene triol: Wanhua Chemical Group Co., Ltd., WANOL R-2304; Zibo Dexin Federal Chemical Industry Co., Ltd., DMN-700, DMN-1000;

[0059] Triethanolamine: BASF-YPC Co., Ltd., TEOA;

[0060] WANOL 1104: Wanhua Chemical Group Co., Ltd., WANOL 1104;

[0061] Filler: Jiangxi Guangyuan Sales Co., Ltd., 800 mesh talc, 400 mesh heavy calcium carbonate, 1250 mesh light calcium carbonate;

[0062] Iron oxide red: Zhejiang Huayuan Pigment Co., Ltd., iron oxide red;

[0063] Acetyl tributyl citrate: Shandong Kexing Chemical Co., Ltd., ATBC;

[0064] Dioctyl terephthalate: Shandong Kexing Chemical Co., Ltd., DOTP;

[0065] Chloropalm oil methyl ester: Dongguan Kuaijie Biotechnology Co., Ltd., RY-110A;

[0066] Zinc neodecanoate: Yantai Sunshine Plastic Co., Ltd., zinc neodecanoate;

[0067] Bismuth neodecanoate: Yantai Sunshine Plastic Co., Ltd., Bismuth neodecanoate;

[0068] Dibutyltin dilaurate: Air Products and Chemicals, T-12;

[0069] Acidic polymer dispersant: Guangzhou Silok Polymer Co., Ltd., Silok-7456F, Silok-7455H;

[0070] Ordinary dispersant (non-acidic polymer dispersant): Guangzhou Silok Polymer Co., Ltd., Silok-7465N;

[0071] UV absorber: Changzhou Xince Polymer Materials, UV-P, UV-1;

[0072] C81: BASF AG, light stabilizer CHIMASSORB 81.

[0073] Example 1

[0074] A reactive thixotropic polyurethane plastic track adhesive is prepared, comprising a component A of a polyurethane prepolymer and a component B of a polyether composite material, wherein the mass ratio of the components A to B is 0.5:1;

[0075] The isocyanate content (NCO%) in component A is 11.8%; the hydroxyl value of component B is 70.0 mgKOH / g.

[0076] In component B, the mass proportion of polyoxypropylene triol (WANOL R-2304) in the polyether polyol is 8%.

[0077] Table 1A component raw materials and addition amount

[0078]

[0079]

[0080] Table 2B Component Raw Materials and Addition Amounts

[0081]

[0082] The adhesive preparation steps include:

[0083] Component A: Fill a reaction flask equipped with a thermometer and a stirrer with nitrogen at a steady flow rate; add isocyanate to the reaction flask, raise the temperature to 80°C and keep it constant, then add polyether polyol; after the addition is complete, react at a constant temperature for 3 hours, test the NCO of the reactant, and stop the reaction when it approaches the theoretical value, and cool to 50°C; add plasticizer and UV absorber, stir for 20 minutes, discharge the material, and seal it for storage.

[0084] Component B: Add polyether polyol and pigment to a reaction flask equipped with a thermometer and a stirrer, and stir evenly for 0.5 h; heat to 100°C, add filler, plasticizer and acidic polymer dispersant, grind and stir for 0.5 h, and continue stirring and dehydrating at a vacuum degree of -0.1 MPa for 2 h; cool to 40°C, add chain extender and catalyst, stir evenly, discharge and seal for storage.

[0085] The above adhesive is used to prepare the plastic track surface material:

[0086] Weigh 50g of component A and 100g of component B into a mixing cup, stir evenly for 2 minutes, then add 150g of EPDM particles with a granularity of 1-3mm and mix evenly; use professional engineering spraying equipment to evenly spray the mixture of glue and particles into a 20cm*20cm*1cm mold within 10 minutes; place the mold in a constant temperature and humidity chamber at 20℃ and 50% humidity for 18 hours to obtain a standard sample of the plastic track surface material with a surface thickness of 2mm.

[0087] The A / B mixed thixotropic ratio is tested according to the plastic track standard GB / T 13354-1992, and the relevant performance is tested according to GB36246-2018.

[0088] Example 2

[0089] A reactive thixotropic polyurethane plastic track adhesive is prepared, comprising a component A of a polyurethane prepolymer and a component B of a polyether composite material, wherein the mass ratio of the components A to B is 0.5:1;

[0090] The isocyanate content (NCO%) in component A is 11.9%; the hydroxyl value of component B is 70.0 mgKOH / g.

[0091] In component B, the mass proportion of polyoxypropylene triol (WANOL R-2304) in the polyether polyol is 6%.

[0092] Table 3A component raw materials and addition amount

[0093]

[0094] Table 4B component raw materials and addition amount

[0095]

[0096]

[0097] The adhesive preparation steps include:

[0098] Component A: Fill a reaction flask equipped with a thermometer and a stirrer with nitrogen at a steady flow rate; add isocyanate to the reaction flask, raise the temperature to 90°C and hold it constant, then add polyether polyol; after the addition is complete, react at a constant temperature for 2.5 hours, test the NCO of the reactant, and stop the reaction when it approaches the theoretical value, and cool to 55°C; add plasticizer and UV absorber, stir for 25 minutes, discharge the material, and seal for storage.

[0099] Component B: Add polyether polyol and pigment to a reaction flask equipped with a thermometer and a stirrer, and stir evenly for 0.7 h; heat to 110°C, add filler, plasticizer and acidic polymer dispersant, grind and stir for 0.7 h, and continue stirring and dehydrating at a vacuum degree of -0.1 MPa for 2.5 h; cool to 45°C, add chain extender and catalyst, stir evenly, discharge and seal for storage.

[0100] The above adhesive was used to prepare the plastic track surface material, and the preparation method was the same as that in Example 1.

[0101] Example 3

[0102] A reactive thixotropic polyurethane plastic track adhesive is prepared, comprising a component A of a polyurethane prepolymer and a component B of a polyether composite material, wherein the mass ratio of the components A to B is 0.5:1;

[0103] The isocyanate content (NCO%) in component A is 11.7%; the hydroxyl value of component B is 68.3 mgKOH / g.

[0104] In component B, the mass proportion of polyoxypropylene triol (WANOL R-2304) in the polyether polyol is 6%.

[0105] Table 5A component raw materials and addition amount

[0106]

[0107]

[0108] Table 6B Component Raw Materials and Addition Amounts

[0109]

[0110] The adhesive preparation steps include:

[0111] Component A: Fill a reaction flask equipped with a thermometer and a stirrer with nitrogen at a steady flow rate; add isocyanate to the reaction flask, raise the temperature to 100°C and hold it constant, then add the polyol; after the addition is complete, react at a constant temperature for 3 hours, test the NCO of the reactant, and stop the reaction when it approaches the theoretical value, and cool to 60°C; add the plasticizer and UV absorber, stir for 30 minutes, discharge the material, and seal it for storage.

[0112] Component B: Add polyether polyol and pigment to a reaction flask equipped with a thermometer and a stirrer, and stir evenly for 1 hour; heat to 120°C, add filler, plasticizer and acidic polymer dispersant, grind and stir for 1 hour, and continue stirring and dehydrating for 3 hours under a vacuum degree of -0.1 MPa; cool to 50°C, add chain extender and catalyst, stir evenly, discharge and seal for storage.

[0113] The above adhesive was used to prepare the plastic track surface material, and the preparation method was the same as that in Example 1.

[0114] Example 4

[0115] A polyurethane plastic track adhesive with reactive thixotropy is prepared, comprising a component A of a polyurethane prepolymer and a component B of a polyether composite material, wherein the mass ratio of the components A to B is 1:1;

[0116] The isocyanate content NCO% in component A is 6.2%; the hydroxyl value of component B is 75.1 mgKOH / g.

[0117] In component B, the mass proportion of polyoxypropylene triol (WANOL R-2304) in the polyether polyol is 8%.

[0118] Table 7A Component Raw Materials and Addition Amounts

[0119]

[0120] Table 8B Component Raw Materials and Addition Amounts

[0121]

[0122] The preparation method of the adhesive is the same as that of Example 1.

[0123] The above adhesive is used to prepare the plastic track surface material:

[0124] Weigh 100g of component A and 100g of component B into a mixing cup, stir evenly for 2 minutes, then add 200g of EPDM particles with a granularity of 1-3mm and mix evenly; use professional engineering spraying equipment to evenly spray the mixture of glue and particles into a 20cm*20cm*1cm mold within 10 minutes; place the mold in a constant temperature and humidity chamber at 20℃ and 50% humidity for 18 hours to obtain a standard sample of the plastic track surface material with a surface thickness of 2mm.

[0125] The A / B mixed thixotropic ratio is tested according to the plastic track standard GB / T 13354-1992, and the relevant performance is tested according to GB36246-2018.

[0126] Example 5

[0127] A polyurethane plastic track adhesive with reactive thixotropy is prepared, comprising a component A of a polyurethane prepolymer and a component B of a polyether composite material, wherein the mass ratio of the components A to B is 1:1;

[0128] The isocyanate content NCO% in component A is 6.2%; the hydroxyl value of component B is 72.0 mgKOH / g.

[0129] In component B, the mass proportion of polyoxypropylene triol (WANOL R-2304) in the polyether polyol is 6%.

[0130] Table 9A component raw materials and addition amount

[0131]

[0132] Table 10B Component Raw Materials and Addition Amounts

[0133]

[0134] The preparation method of the adhesive is the same as that of Example 2, and the preparation method of the plastic track surface material is the same as that of Example 4.

[0135] Example 6

[0136] A polyurethane plastic track adhesive with reactive thixotropy is prepared, comprising a component A of a polyurethane prepolymer and a component B of a polyether composite material, wherein the mass ratio of the components A to B is 1:1;

[0137] The isocyanate content NCO% in component A is 6.1%; the hydroxyl value of component B is 74.3 mgKOH / g.

[0138] In component B, the mass proportion of polyoxypropylene triol (WANOL R-2304) in the polyether polyol is 5%.

[0139] Table 11A component raw materials and addition amount

[0140]

[0141] Table 12B Component Raw Materials and Addition Amounts

[0142]

[0143] The method for preparing the adhesive is the same as that in Example 3, and the method for preparing the plastic track surface material is the same as that in Example 4.

[0144] Comparative Example 1

[0145] The preparation method was similar to that in Example 4, except that the polyoxypropylene triol WANOL R-2304 was omitted from the polyether polyol of component B, the polyether triol WANOL F3135 was added in an amount of 12 g, the polyether diol WANOL DL-1000D was added in an amount of 16 g, and the chain extender WANOL 1104 was added in an amount of 5 g. Other operations remained unchanged to prepare an adhesive.

[0146] Comparative Example 2

[0147] The adhesive was prepared by referring to the preparation method of Example 4, except that the acidic polymer dispersant was not added to component B and other operations remained unchanged.

[0148] Comparative Example 3

[0149] The adhesive was prepared by referring to the preparation method of Example 4, except that the acidic polymer dispersant in component B was replaced with a common dispersant Silok-7465N, and other operations remained unchanged.

[0150] According to the plastic track standard GB / T 13354-1992, the A / B mixed thixotropic ratio is tested. After mixing component A and component B, the same rotor is used and the speed is tested with a 10-fold difference. That is, the viscosity value at a lower speed is higher than the viscosity value at a higher speed.

[0151] According to the plastic track standard GB36246-2018, the operating time and curing time are tested:

[0152] Working time: After mixing component A and component B, the time it takes for obvious tooth marks to appear on the surface after "scraping". The plastic track industry requires that it can be naturally leveled within 20 minutes without obvious tooth marks;

[0153] Curing time: The time it takes for components A and B to fully cure and withstand being stepped on by an adult male without noticeable deformation. The plastic track industry requires complete curing within 24 hours for normal use.

[0154] The tensile strength is tested according to the test method of the plastic track standard GB / T 10654-2001.

[0155] The shear strength was tested according to the test method of national standard GB / T7124.

[0156] The test results of Examples 1 to 6 and Comparative Examples 1 to 2 are shown in the following table:

[0157] Table 13 Performance test results of the embodiments of the present invention

[0158]

[0159] Table 13 shows that the polyurethane plastic track adhesive described in this invention exhibits excellent thixotropic properties and a long working time. After mixing components A and B, thanks to the absence of amine chain extenders in the system and the effective suppression of adhesive activity by the acidic dispersant, the synergistic effect results in a relatively mild initial reaction, providing ample working time of 20-25 minutes for construction and effectively avoiding the risk of pipe blockage. Furthermore, the rapid increase in the static viscosity of the system within a short period of time successfully addresses the problem of particle "leakage" caused by excessive flow during construction.

[0160] Compared with traditional thixotropic polyurethane adhesives, the reactive thixotropic polyurethane adhesive prepared by the method of the present invention does not use any external thixotropic agent or filler and aromatic amine reactant, and is more in line with the environmental protection requirements in the field of plastic tracks.

Claims

1. A reactive thixotropic polyurethane plastic track adhesive, characterized in that: The method comprises a polyurethane prepolymer component A and a polyether component B, wherein the mass ratio of component A to component B is 0.5 to 2:1; The polyurethane prepolymer of component A comprises the following components by weight: The polyether composition of component B comprises the following components by weight: In component B, the polyether polyol comprises at least one polyether polyol having a functionality of 3 and a molecular weight of less than 1000 g / mol; its mass proportion is 2 to 15%, based on the total mass of the polyether composition in component B being 100%.

2. The adhesive according to claim 1, characterized in that The mass ratio of component A to component B is 0.5 to 1:

1.

3. The adhesive according to claim 1, characterized in that The polyurethane prepolymer of component A comprises the following components by weight:

4. The adhesive according to claim 1, characterized in that The polyether composition of component B comprises the following components by weight:

5. The adhesive according to claim 1, wherein In component B, the polyether polyol comprises at least one polyether polyol having a functionality of 3 and a molecular weight of less than 400 to 700 g / mol.

6. The adhesive according to claim 1, characterized in that In component B, the polyether polyol comprises at least one polyether polyol with a functionality of 3 and a molecular weight less than 1000 g / mol, which accounts for 5 to 10% by mass, based on the total mass of the polyether composition in component B being 100%.

7. The adhesive according to claim 1, wherein The isocyanate content NCO% in the A component is 4 to 20 wt%; The hydroxyl value of the B component is 50 to 130 mgKOH / g.

8. The adhesive according to claim 1, wherein The isocyanate content (NCO%) in the component A is 6 to 12 wt%.

9. The adhesive according to claim 1, wherein The hydroxyl value of the B component is 60 to 80 mgKOH / g.

10. The adhesive according to claim 1, wherein In the polyurethane prepolymer of component A, the isocyanate is selected from one or more of 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate; In the polyurethane prepolymer of component A, the polyether polyol is selected from one or more of a polyether polyol having a molecular weight of 1000 to 5000 g / mol, a functionality of 2, and a hydroxyl value of 20 to 120 mgKOH / g and a polyether polyol having a molecular weight of 3000 to 6000 g / mol, a functionality of 3, and a hydroxyl value of 25 to 60 mgKOH / g.

11. The adhesive according to claim 10, characterized in that The isocyanate is selected from one or more of WANOL MDI-50FB, WANOL MDI-100F, and WANOL PM200.

12. The adhesive according to claim 10, characterized in that The polyether polyol is selected from one or more of polyethylene oxide unsaturated polyols and polypropylene oxide unsaturated polyols.

13. The adhesive according to claim 12, characterized in that The polyether polyol is selected from one or more of WANOL DL-1000D, WANOL DL-2000, WANOL DL-4000D, WANOL 2130, WANOL 2140F, WANOL F3128, WANOL F3135, and WANOL F3156.

14. The adhesive according to claim 1, wherein In the polyurethane prepolymer of component A, the plasticizer is selected from one or more of C17-C24 long-chain chlorinated paraffin, chloropalm oil methyl ester, dioctyl terephthalate and acetyl tributyl citrate; In the polyurethane prepolymer of component A, the ultraviolet absorber is selected from a high-efficiency ultraviolet absorber of the benzotriazole type that can absorb ultraviolet rays with a wavelength of 270 to 340 nm.

15. The adhesive according to claim 14, characterized in that The plasticizer is acetyl tributyl citrate.

16. The adhesive according to claim 14, characterized in that The ultraviolet absorber is selected from one or more of UV-P, UV-1, and C81.

17. The adhesive according to claim 1, wherein In the polyether composition of component B, the polyether polyol comprises polyoxypropylene triol having a functionality of 3, a molecular weight of 400 g / mol, and a hydroxyl value of 420 mgKOH / g.

18. The adhesive according to claim 17, characterized in that The polyether polyol comprises WANOLR-2304.

19. The adhesive according to claim 1, wherein The polyether polyol further comprises one or more of other polyether polyols having a molecular weight of 1000-5000 g / mol, a functionality of 2, a hydroxyl value of 20-120 mgKOH / g and a molecular weight of 3000-6000 g / mol, a functionality of 3, and a hydroxyl value of 25-60 mgKOH / g.

20. The adhesive according to claim 19, characterized in that The other polyether polyols also include conventional polyethers with PO chain extension or PO chain extension and EO end-capping.

21. The adhesive according to claim 20, characterized in that The other polyether polyols are one or more of polyethylene oxide unsaturated polyols and polypropylene oxide unsaturated polyols.

22. The adhesive according to claim 21, characterized in that The other polyether polyols include WANOL DL-1000D, WANOL DL-2000, WANOL DL-4000D, WANOL 2130, WANOL 2140F, WANOL F3128, WANOL F3135 and WANOL F3156.

23. The adhesive according to claim 1, wherein In the polyether component B, the chain extender is selected from one or more of a polyurethane chain extender, diethylene glycol and triethanolamine; In the polyether composition of component B, the filler is one or more of 400-1000 mesh heavy calcium carbonate, 400-1000 mesh talc, and 400-1250 mesh light calcium carbonate; In the polyether composition of component B, the pigment is selected from iron oxide red, iron oxide green or phthalocyanine blue; In the polyether composition of component B, the plasticizer is one or more of C17-C24 long-chain chlorinated paraffin, chloropalm oil methyl ester, dioctyl terephthalate and acetyl tributyl citrate; In the polyether composition of component B, the acidic polymer dispersant is a carboxylate block polymer with a viscosity greater than 1000 cps and an acid value of 50 to 200 mgKOG / g; In the polyether composition of component B, the catalyst is selected from one or more of dibutyltin dilaurate, didodecylthiodibutyltin, bismuth neodecanoate, bismuth isooctanoate, zinc neodecanoate and zinc isooctanoate.

24. The adhesive according to claim 23, characterized in that The chain extender is WANOL 1104.

25. The adhesive according to claim 23, characterized in that The filler is one or more of 400-800 mesh heavy calcium carbonate, 600-800 mesh talc, and 800-1250 mesh light calcium carbonate.

26. The adhesive according to claim 23, characterized in that The plasticizer is acetyl tributyl citrate.

27. The adhesive according to claim 23, characterized in that The carboxylate block polymer has a viscosity of 2000 to 5000 cps and an acid value of 50 to 80 mgKOG / g.

28. The adhesive according to claim 23, wherein The carboxylate block polymer is selected from one or more of carboxylate block copolymers and polyacid ester block copolymers.

29. The adhesive according to claim 28, characterized in that The carboxylate block polymer is selected from Silok-7456F and Silok-7455H.

30. A method for preparing the reactive thixotropic polyurethane adhesive according to any one of claims 1 to 29, characterized in that the steps include: 1) Preparation of component A polyurethane prepolymer: Mix isocyanate and polyether polyol, react at 80-100°C for 2-3 hours until NCO is close to the theoretical value, then stop the reaction, cool to 50-60°C, add plasticizer and UV absorber, stir for 20-30 minutes to mix evenly, discharge and seal with nitrogen for storage; 2) Preparation of component B polyether combination material: Mix the polyether polyol and pigment, stir for 0.5 to 1 hour to make the mixture uniform, heat to 100 to 120°C, add filler, plasticizer and acidic polymer dispersant, grind and stir for 0.5 to 1 hour, vacuum dehydrate for 2 to 3 hours to reduce the water content to below 100 ppm, cool to 40 to 50°C, then add chain extender and catalyst, stir evenly and seal for storage.

31. The preparation method according to claim 30, characterized in that In step 1), isocyanate and polyether polyol are mixed and reacted at 80-85°C.

32. Use of the reactive thixotropic polyurethane adhesive according to any one of claims 1 to 29 in plastic track sports surface materials.

33. A plastic track surface material, comprising the reactive thixotropic polyurethane adhesive according to any one of claims 1 to 29 and EPDM particles in a mass ratio of 1:0.5 to 2.

34. The plastic track surface material according to claim 33, characterized in that: The reactive thixotropic polyurethane adhesive and EPDM particles are prepared in a mass ratio of 1:1 to 1.

5.

35. The plastic track surface material according to claim 33, characterized in that: The EPDM particles have a particle size of 1 to 4 mm and are selected from the Mele rubber particles produced by Guangdong Chuanao High-tech Technology Co., Ltd.

36. The plastic track surface material according to claim 33, characterized in that: The EPDM particles have a particle size of 1 to 3 mm.

37. The plastic track surface material according to claim 33, characterized in that: The plastic track surface material has a thixotropic index of more than 4, an operating time of 20 to 25 minutes, and a room temperature curing time of less than 24 hours.

38. A method for preparing the plastic track surface material according to any one of claims 33 to 37, characterized in that: The steps are: mix and stir the polyurethane prepolymer component A and the polyether component B in the reactive thixotropic polyurethane adhesive for 1 to 2 minutes, then mix and stir evenly with EPDM particles, and spray them on the elastic base layer of the plastic track within 10 minutes to form a surface layer.

39. The method for preparing the plastic track surface material according to claim 38, characterized in that: The thickness of the surface layer is 2 to 3 mm.

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