Environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive and preparation method thereof

Abstract

The invention discloses an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive and a preparation method thereof, which solves the problems of insufficient compatibility and mechanical strength of a plastic runway prepared by using organosilicon modified polyurethane in the existing process, and easy shedding or stratification when the organosilicon is compounded with the polyurethane. The runway surface adhesive is composed of the following raw materials: water-based polyurethane emulsion, modified acrylate, modifier, flame retardant, antioxidant, crosslinking agent, auxiliary foaming agent and white oil. The invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, which uses water-based polyurethane emulsion and modified acrylate as base materials, and the method of modifying the water-based polyurethane emulsion by modified acrylate is more environmentally friendly, while the modifier in the raw materials ensures that the runway surface adhesive has high elasticity and crosslinking density, and the modifier and the auxiliary foaming agent cooperate with each other to significantly improve the foaming effect of the plastic runway, and help to generate uniform and dense bubbles inside the runway surface adhesive material.

Description

Technical Field

[0001] The invention belongs to the technical field of runways, and in particular relates to an environmentally friendly high-elastic polyurethane-modified acrylic runway surface adhesive and a preparation method thereof. Background Art

[0002] The plastic track is an indispensable and important facility in modern track and field venues. Compared with the traditional soil track, it has good elasticity, anti-slip, wear resistance, shock absorption, easy site maintenance, bright colors, beautiful and neat appearance, etc. The polyurethane plastic track is a high-performance track material widely used in track and field venues and sports venues. The polyurethane plastic track is composed of polyurethane prepolymer, mixed polyether, waste tire rubber, EPDM rubber particles or PU particles, pigments, additives and fillers. It has the characteristics of good flatness, high compressive strength, appropriate hardness and elasticity, and stable physical properties, which is conducive to the athletes' speed and technology. Acrylic resin is an important synthetic polymer material, widely used in coatings, adhesives, textiles and construction and other fields. Acrylate-modified water-based polyurethane has the advantages of strong wear resistance, strong corrosion resistance, high mechanical properties, high brightness and good water resistance, and has been widely used in track materials in track and field venues and sports venues.

[0003] Chinese patent CN113321449A discloses a manufacturing process of silicon PU for plastic runway, which includes, from bottom to top, a silicone-modified polyurethane elastic material layer, an anti-skid layer and a modified acrylic surface layer, wherein the silicone-modified polyurethane elastic material layer includes a mixed type adhesive layer and a full-rubber type adhesive layer, and the manufacturing process of silicon PU for plastic runway includes the following steps: first preparing adhesive slurry; pouring the adhesive slurry into an asphalt concrete base layer, adding elastic rubber particles, and forming a mixed type adhesive layer as a lower layer after curing, and then pouring the adhesive slurry onto the lower mixed type adhesive layer, spreading it flat, and forming an upper layer of the full-rubber type adhesive layer after curing, to prepare a silicone-modified polyurethane elastic material layer with a double-layer structure; coating modified acrylic on the anti-skid layer to form a modified acrylic surface layer, to prepare the silicon PU for plastic runway. However, the existing process of using silicone-modified polyurethane to prepare plastic tracks has insufficient compatibility and mechanical strength. When silicone and polyurethane are compounded, they are prone to falling off or stratification, and the mechanical strength of silicone itself is relatively low, which causes the silicone / polyurethane composite material to easily agglomerate or be damaged when subjected to external forces, reducing the elasticity and comfort of the material. To address the above problems, we proposed an environmentally friendly, highly elastic polyurethane-modified acrylic track surface adhesive and a preparation method thereof. Summary of the invention

[0004] The purpose of the present invention is to provide an environmentally friendly high-elastic polyurethane modified acrylic track surface adhesive and a preparation method thereof in view of the deficiencies in the prior art, so as to solve the problems that the compatibility and mechanical strength of the plastic track prepared by the prior art process using silicone modified polyurethane are insufficient, and when the silicone and polyurethane are compounded, they are prone to falling off or stratification, and the mechanical strength of the silicone itself is relatively low, resulting in the silicone / polyurethane composite material being prone to agglomeration or damage when subjected to external forces, thereby reducing the elasticity and comfort of the material.

[0005] The present invention is achieved in this way: an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive comprises the following raw materials in parts by weight: 50-110 parts of aqueous polyurethane emulsion, 40-65 parts of modified acrylate, 10-40 parts of modifier, 10-18 parts of flame retardant, 1-15 parts of antioxidant, 10-20 parts of cross-linking agent, 1-10 parts of auxiliary foaming agent, and 20-30 parts of white oil.

[0006] Preferably, the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive comprises the following raw materials in parts by weight: 60-100 parts of aqueous polyurethane emulsion, 45-60 parts of modified acrylate, 15-30 parts of modifier, 12-16 parts of flame retardant, 4-12 parts of antioxidant, 12-17 parts of cross-linking agent, 3-9 parts of auxiliary foaming agent, and 22-28 parts of white oil.

[0007] Preferably, the aqueous polyurethane emulsion comprises the following raw materials in weight percentage:

[0008] Polyoxypropylene glycol: 30%;

[0009] Isophorone diisocyanate: 25%;

[0010] 1,6-hexamethylene diisocyanate: 5%;

[0011] Polyethylene glycol: 30%;

[0012] Stannous oxalate: 5%;

[0013] Bismuth isooctanoate: 5%;

[0014] Wherein, the modified acrylate comprises the following raw materials in weight percentage:

[0015] Methyl methacrylate: 30%;

[0016] Maleic rosin glycol acrylate: 5%;

[0017] Isobornyl methacrylate: 15%;

[0018] 2-Amino-1,3-propanediol: 10%;

[0019] Methyltrimethoxysilane: 15%;

[0020] Octamethylcyclotetrasiloxane: 15%;

[0021] Surfactant: 5%;

[0022] Emulsifier: 5%.

[0023] The preparation method of the aqueous polyurethane emulsion specifically comprises:

[0024] Add polyoxypropylene glycol, isophorone diisocyanate and 1,6-hexamethylene diisocyanate into a three-necked flask, mechanically stir the polyoxypropylene glycol, isophorone diisocyanate and 1,6-hexamethylene diisocyanate at a stirring speed of 100-150 r / min, control the temperature at 85-92°C, and stir for 60 minutes;

[0025] Add polyethylene glycol, stannous oxalate and bismuth isooctanoate into a three-necked flask in sequence, adjust the temperature of the three-necked flask to 70-75° C., and stir and mix for 100 minutes;

[0026] Acetone was added into the three-necked flask to dilute the reactants in the three-necked flask, and then hydroxypropyl acrylate was added for end-capping. The reaction was kept at 70° C. for 60 minutes. The three-necked flask was cooled to room temperature, deionized water was added into the three-necked flask and stirred to disperse, and then the acetone was removed to obtain a waterborne polyurethane emulsion.

[0027] The preparation method of the modified acrylate specifically comprises:

[0028] Acetone was placed in a four-necked flask, which was placed in a constant temperature water bath. The four-necked flask was vacuumed for 30 minutes at 50°C, methyl methacrylate and lauroyl peroxide were added, stirred and mixed for 20 minutes, and then allowed to stand for 5 minutes.

[0029] Add maleic rosin ethylene glycol acrylate into a four-necked flask, stir the four-necked flask with a magnetic stirrer, and control the stirring speed to 50-80 r / min. Heat the four-necked flask to 60° C. and keep the temperature for 60 minutes to obtain an oil phase mixture;

[0030] The surfactant was compounded with an equal volume of anhydrous ethanol, and an equal volume of cocamidopropyl betaine and sodium lauryl sulfate was used to form a surfactant. Three times the volume of deionized water was added to the surfactant and anhydrous ethanol compound solution to obtain a surfactant dilution. The surfactant dilution was injected into a magnetic stirrer and stirred for 20 minutes. The magnetic stirrer heated the surfactant dilution to 60°C.

[0031] The surfactant dilution is placed in the oil phase mixture, and a condenser and a reflux tube are installed in the four-necked flask containing the oil phase mixture, and the surfactant dilution and the oil phase mixture are stirred and mixed, and the four-necked flask is heated to 80° C. and kept warm for 100 minutes, and then the four-necked flask is heated to 95° C. and kept warm for 120 minutes. After the reaction, the reaction is allowed to stand for 3 hours, and the reaction product is washed with water and passed through a 30-mesh sieve plate to remove impurities to obtain a first modified component;

[0032] Isobornyl methacrylate, 2-amino-1,3-propanediol and acetonitrile are placed in a reaction kettle and mixed, nitrogen is introduced into the reaction kettle for protection, the reaction kettle is stirred for reaction, the stirring speed is 100-150r / min, the reaction kettle temperature is 65-70°C, the reaction time is 7-8h, and a diol containing isobornyl methacrylate and an amino group is obtained;

[0033] Add methyltrimethoxysilane and octamethylcyclotetrasiloxane into a reaction container, add tetradecyltrimethylammonium chloride into the reaction container, stir the reaction container at a speed of 150-200 r / min for 40 minutes, add ammonia water into the reaction container, and stir for 10 minutes;

[0034] Putting a diol containing methacrylic acid isobornyl and amino groups into a reaction container, stirring at room temperature for 50 minutes, to obtain a second modified component;

[0035] The first modified component and the second modified component were placed in a reaction kettle, and an emulsifier was added dropwise to the reaction kettle. The emulsifier was SE-10 emulsifier, and the mixture was stirred for 40 minutes to obtain modified acrylate.

[0036] Preferably, the modifier comprises the following raw materials in weight percentage:

[0037] Coconut oil: 30%;

[0038] Acetic acid: 10%;

[0039] Dibutyltin laurate: 5%;

[0040] Graphene oxide: 30%;

[0041] Polyethyleneimine: 25%;

[0042] The preparation method of the modifier specifically comprises:

[0043] Take coconut oil and acetic acid, put them in a three-necked flask, the three-necked flask is equipped with a magnetic stirrer, a condenser, and a reflux tube, put the three-necked flask in a 50°C oil bath and heat it for 20 minutes, and the stirring speed of the magnetic stirrer is 100-120r / min;

[0044] Hydrogen peroxide and concentrated sulfuric acid were added dropwise into a three-necked flask, with the mass ratio of coconut oil, hydrogen peroxide and concentrated sulfuric acid being 1:0.5-0.6:0.002-0.003. After the addition was completed, the temperature of the oil bath was adjusted to 70°C, and the reaction was continued for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the aqueous phase in the three-necked flask was separated;

[0045] Take equal volumes of methanol and hydrochloric acid and place them in a three-necked flask, the mass ratio of methanol to coconut oil is 0.2:1, condense and reflux for reaction at 65°C for 2h, cool to room temperature, separate the water phase in the three-necked flask, and obtain coconut oil polyol;

[0046] Place dibutyltin laurate and coconut oil polyol in a round-bottom flask, introduce nitrogen into the round-bottom flask for protection, stir the mixture in the round-bottom flask, react at 65° C. for 30 minutes, and stand for 30 minutes to obtain a coconut oil polyol mixture for standby use;

[0047] Take graphene oxide, add graphene oxide into a reactor, pass nitrogen into the reactor for protection, add 10 times the volume of deionized water into the reactor, stir at 80° C. for 3 h, add polyethyleneimine into the reactor, stir at 85° C. for 3 h, cool the reactor to room temperature, place the mixture in the reactor in a centrifuge for centrifugation, the speed of the centrifuge is 8000-8500 r / min, and after centrifugation for 30 min, obtain modified graphene;

[0048] The modified graphene was mixed with a coconut oil polyol mixture, stirred at 75° C. for 40 min, then heated to 60° C. and subjected to ultrasound for 35 min to obtain a modifier.

[0049] Preferably, the auxiliary foaming agent comprises the following raw materials in weight percentage:

[0050] Tetraethyl orthosilicate: 40%;

[0051] Copper sulfate: 20%;

[0052] Hydrazine hydrate: 20%;

[0053] Ammonia water: 10%;

[0054] Ethanol: 10%;

[0055] The preparation method of the auxiliary foaming agent specifically comprises:

[0056] Using tetraethyl orthosilicate as a silicon source and ammonia water as a catalyst, ammonia water and ethanol are placed in a reaction kettle and mixed at room temperature, stirred at a stirring speed of 150-200 r / min for 30 minutes, tetraethyl orthosilicate is added dropwise to the reaction kettle, and stirring is continued for 3 hours to obtain a silicon dioxide dispersion;

[0057] Taking a silica dispersion, heating the silica dispersion to 45° C., then adding a copper sulfate solution to the silica dispersion, stirring at 300 r / min for 2 h, and filtering the silica dispersion to obtain a silica filter cake loaded with copper ions;

[0058] With hydrazine hydrate as a reducing agent, a silica filter cake is placed in a reaction kettle, the silica filter cake is dispersed in 10 times the volume of deionized water, heated to 70°C, a sodium hydroxide solution is used to adjust the pH value of the reaction kettle to 10-10.2, hydrazine hydrate is added to the reaction kettle, reacted for 2 hours, filtered, the filter cake is washed with deionized water for 3-5 times, ground into powder, and an auxiliary foaming agent is obtained.

[0059] Preferably, the flame retardant is a mixture of antimony trioxide and expandable graphite, and the mass ratio of antimony trioxide to expandable graphite is 1:2.

[0060] Preferably, the antioxidant is antioxidant RD, the cross-linking agent is a mixture of maleopimaric acid ethylene glycol acrylate and dicumyl peroxide, and the mass ratio of maleopimaric acid ethylene glycol acrylate to dicumyl peroxide is 1:1.

[0061] On the other hand, the present invention also provides a method for preparing an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, the method for preparing an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive specifically comprising:

[0062] Place the modifier and modified acrylate in a reaction kettle, control the reaction temperature to 60-65°C, and stir at a stirring speed of 200 r / min for 30 min;

[0063] Add waterborne polyurethane emulsion into the reactor, stir at 70°C for 1 hour, drop acetone into the reactor at a rate of one drop every 3-5 seconds, continue the reaction for 2 hours, add crosslinking agent into the reactor, stir and mix with a stirrer at 500 r / min for 40 minutes to obtain a crosslinked mixture;

[0064] The flame retardant, antioxidant, auxiliary foaming agent and white oil were placed in a round-bottom flask for mixing, and the round-bottom flask was placed in an 80°C oil bath for stirring for 40 minutes. The reactants in the round-bottom flask were placed in a non-pulse type microwave reactor, and the non-pulse type microwave reactor was started for microwave reaction for 30 minutes to obtain a microwave mixture;

[0065] The cross-linked mixture and the microwave mixture were placed in a reactor for mixing and dispersed at high speed for 20 minutes. The temperature of the reactor was 70° C. The cross-linked mixture and the microwave mixture were centrifuged at a speed of 5000-5500 r / min for 10 minutes to obtain a polyurethane modified acrylic runway surface adhesive.

[0066] Compared with the prior art, the embodiments of the present application have the following beneficial effects:

[0067] The embodiment of the present invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, which uses water-based polyurethane emulsion and modified acrylate as base materials. The method of modifying the water-based polyurethane emulsion by modified acrylate is more environmentally friendly, and the hydrophobicity and heat resistance of the runway surface adhesive are also improved. The modifier in the raw material ensures that the runway surface adhesive has high elasticity and cross-linking density. The synergistic cooperation of the modifier and the auxiliary foaming agent not only helps to improve the wear resistance, aging resistance and UV resistance of the plastic runway, but also can significantly improve the foaming effect of the plastic runway, which helps to produce uniform and dense bubbles inside the runway surface adhesive material, avoids the agglomeration of the runway surface adhesive, thereby improving the elasticity and comfort of the plastic runway, and ensuring the environmental performance of the plastic runway.

[0068] In an embodiment of the present invention, a method for preparing an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive is also provided. When preparing the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, the modifier, modified acrylate, and water-based polyurethane are mixed to achieve the combined modification of the water-based polyurethane by the modifier and modified acrylate, thereby significantly improving the weather resistance of the polyurethane material and ensuring that the runway surface adhesive has both the weather resistance and light stability of the polyacrylate itself, and can also effectively resist ultraviolet rays and oxidation, thereby slowing down the aging of the material.

[0069] In the embodiment of the present invention, an aqueous polyurethane emulsion and a preparation method thereof are provided. The aqueous polyurethane emulsion uses polyoxypropylene glycol, isophorone diisocyanate, and 1,6-hexamethylene diisocyanate as raw materials, so that the prepared aqueous polyurethane emulsion has lower toxicity and better mechanical properties. The use of stannous oxalate and bismuth isooctanoate as catalysts further ensures that the aqueous polyurethane emulsion has lower toxicity and better hydrolysis resistance stability, while also providing good fluidity and foam openness, which helps to improve the performance of the aqueous polyurethane emulsion.

[0070] In an embodiment of the present invention, a modifier and a preparation method thereof are provided. The modifier uses coconut oil as a raw material to ensure the flexibility and high elasticity of the modifier. Polyethyleneimine is then used as a modifier to modify graphene oxide, so that the graphene oxide has better dispersibility and matrix compatibility. The modifier acts on waterborne polyurethane, so that the thermal stability, tensile strength and shape memory properties of the waterborne polyurethane are significantly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Figure 1 It is a schematic diagram of the implementation process of the method for preparing the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive provided by the present invention.

[0072] Figure 2The present invention is a schematic diagram of the process for preparing the aqueous polyurethane emulsion.

[0073] Figure 3 It is a schematic diagram of the implementation process of the method for preparing modified acrylate provided by the present invention.

[0074] Figure 4 It is a schematic diagram of the implementation process of the method for preparing the modifier provided by the present invention.

[0075] Figure 5 It is a schematic diagram of the implementation process of the method for preparing the auxiliary foaming agent provided by the present invention.

[0076] Figure 6 It is a structural schematic diagram of the method for preparing the auxiliary foaming agent provided by the present invention.

[0077] Figure 7 It is a schematic diagram of the elongation at break test results of Examples 1-5 of the present invention and Comparative Examples 1-5.

[0078] Figure 8 It is a schematic diagram of the flame retardancy test results provided by the present invention.

[0079] Fig. 9 It is a schematic diagram of the thermogravimetric analysis test results provided by the present invention. DETAILED DESCRIPTION

[0080] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by technicians in the technical field of this application; the terms used in the specification of the application herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in the specification and claims of this application and the above-mentioned drawings are intended to cover non-exclusive inclusions. The terms "first", "second", etc. in the specification and claims of this application or the above-mentioned drawings are used to distinguish different objects, not to describe a specific order.

[0081] The existing process of using silicone-modified polyurethane to prepare plastic tracks has insufficient compatibility and mechanical strength. When silicone is compounded with polyurethane, it is easy to fall off or delaminate, and the mechanical strength of silicone itself is relatively low, which causes the silicone / polyurethane composite material to easily agglomerate or be damaged when subjected to external forces, reducing the elasticity and comfort of the material. In response to the above problems, we proposed an environmentally friendly high-elastic polyurethane modified acrylic track surface adhesive and a preparation method thereof. The environmentally friendly high-elastic polyurethane modified acrylic track surface adhesive is composed of the following raw materials: water-based polyurethane emulsion, modified acrylate, modifier, flame retardant, antioxidant, cross-linking agent, auxiliary foaming agent, and white oil. The embodiment of the present invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, which uses water-based polyurethane emulsion and modified acrylic ester as base materials. The method of modifying the water-based polyurethane emulsion by modified acrylic ester is more environmentally friendly, and the hydrophobicity and heat resistance of the runway surface adhesive are also improved. The modifier in the raw material ensures that the runway surface adhesive has high elasticity and cross-linking density. The synergistic cooperation of the modifier and the auxiliary foaming agent not only helps to improve the wear resistance, aging resistance and UV resistance of the plastic runway, but also can significantly improve the foaming effect of the plastic runway, which is helpful for the runway surface adhesive. Uniform and dense bubbles are generated inside the material to prevent the track surface rubber from agglomerating, thereby improving the elasticity and comfort of the plastic track and ensuring the environmental performance of the plastic track. The problem that the existing process of using silicone-modified polyurethane to prepare plastic tracks has insufficient compatibility and mechanical strength, and that silicone and polyurethane are prone to falling off or stratification when compounded, and that the mechanical strength of silicone itself is relatively low, causes the silicone / polyurethane composite material to easily agglomerate or be damaged when subjected to external forces, reducing the elasticity and comfort of the material.

[0082] Example 1

[0083] An embodiment of the present invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, which includes the following raw materials in parts by weight: 50 parts of aqueous polyurethane emulsion, 40 parts of modified acrylate, 10 parts of modifier, 10 parts of flame retardant, 1 part of antioxidant, 10 parts of cross-linking agent, 1 part of auxiliary foaming agent, and 20 parts of white oil.

[0084] In this embodiment, the aqueous polyurethane emulsion includes the following raw materials in weight percentage: polyoxypropylene glycol: 30%; isophorone diisocyanate: 25%; 1,6-hexamethylene diisocyanate: 5%; polyethylene glycol: 30%; stannous oxalate: 5%; bismuth isooctanoate: 5%;

[0085] The modified acrylic ester includes the following raw materials in weight percentage: methyl methacrylate: 30%; maleated rosin glycol acrylate: 5%; isobornyl methacrylate: 15%; 2-amino-1,3-propanediol: 10%; methyltrimethoxysilane: 15%; octamethylcyclotetrasiloxane: 15%; surfactant: 5%; emulsifier: 5%.

[0086] In an embodiment of the present invention, a method for preparing an environmentally friendly high-elastic polyurethane-modified acrylic runway surface adhesive is also provided, such as Figure 1 As shown, the preparation method of the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive specifically includes:

[0087] Step S10, placing the modifier and modified acrylate in a reaction kettle, controlling the reaction temperature to 60-65° C., and stirring at a stirring speed of 200 r / min for 30 min;

[0088] In this embodiment, the reactor model can be a stainless steel electric heating reactor, and the reactor has a built-in material distributor, so that the material can be evenly distributed in a very short time to prevent the material from agglomerating due to lack of time to cool down when it is concentrated.

[0089] Step S20, adding water-based polyurethane emulsion into the reaction kettle, stirring at 70° C. for 1 h, dropping acetone into the reaction kettle at a rate of one drop every 3-5 seconds, continuing the reaction for 2 h, adding a crosslinking agent into the reaction kettle, stirring and mixing with a stirrer at 500 r / min for 40 min, to obtain a crosslinked mixture;

[0090] Step S30, taking a flame retardant, an antioxidant, an auxiliary foaming agent, and white oil and placing them in a round-bottom flask to mix, and placing the round-bottom flask in an 80° C. oil bath and stirring for 40 minutes, placing the reactants in the round-bottom flask in a non-pulse type microwave reactor, and starting a microwave reaction in the non-pulse type microwave reactor for 30 minutes to obtain a microwave mixture;

[0091] It should be noted that the non-pulse microwave reactor model is a MAS-1 non-pulse microwave reactor (Shanghai Xinyi Microwave Chemistry Technology Co., Ltd.), the microwave frequency is 2500 MHz, and the oil bath pot is a HH-4 (Changzhou Kaihang Instrument) oil bath pot.

[0092] Step S40, taking the cross-linked mixture and the microwave mixture and placing them in a reactor for mixing, high-speed shear dispersion for 20 minutes, the reactor temperature is 70°C, and the cross-linked mixture and the microwave mixture are centrifuged at a speed of 5000-5500 r / min for 10 minutes to obtain a polyurethane modified acrylic runway surface adhesive.

[0093] In an embodiment of the present invention, a method for preparing an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive is also provided. When preparing the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, the modifier, modified acrylate, and water-based polyurethane are mixed to achieve the combined modification of the water-based polyurethane by the modifier and modified acrylate, thereby significantly improving the weather resistance of the polyurethane material and ensuring that the runway surface adhesive has both the weather resistance and light stability of the polyacrylate itself, and can also effectively resist ultraviolet rays and oxidation, thereby slowing down the aging of the material.

[0094] Example 2

[0095] An embodiment of the present invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, which includes the following raw materials in parts by weight: 110 parts of aqueous polyurethane emulsion, 65 parts of modified acrylate, 40 parts of modifier, 18 parts of flame retardant, 15 parts of antioxidant, 20 parts of cross-linking agent, 10 parts of auxiliary foaming agent, and 30 parts of white oil.

[0096] In this embodiment, the aqueous polyurethane emulsion includes the following raw materials in weight percentage: polyoxypropylene glycol: 30%; isophorone diisocyanate: 25%; 1,6-hexamethylene diisocyanate: 5%; polyethylene glycol: 30%; stannous oxalate: 5%; bismuth isooctanoate: 5%;

[0097] The modified acrylic ester includes the following raw materials in weight percentage: methyl methacrylate: 30%; maleated rosin glycol acrylate: 5%; isobornyl methacrylate: 15%; 2-amino-1,3-propanediol: 10%; methyltrimethoxysilane: 15%; octamethylcyclotetrasiloxane: 15%; surfactant: 5%; emulsifier: 5%.

[0098] In an embodiment of the present invention, a method for preparing an environmentally friendly high-elastic polyurethane-modified acrylic runway surface adhesive is also provided, such as Figure 1 As shown, the preparation method of the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive specifically includes:

[0099] Step S10, placing the modifier and modified acrylate in a reaction kettle, controlling the reaction temperature to 60-65° C., and stirring at a stirring speed of 200 r / min for 30 min;

[0100] Step S20, adding water-based polyurethane emulsion into the reaction kettle, stirring at 70° C. for 1 h, dropping acetone into the reaction kettle at a rate of one drop every 3-5 seconds, continuing the reaction for 2 h, adding a crosslinking agent into the reaction kettle, stirring and mixing with a stirrer at 500 r / min for 40 min, to obtain a crosslinked mixture;

[0101] Step S30, taking a flame retardant, an antioxidant, an auxiliary foaming agent, and white oil and placing them in a round-bottom flask to mix, and placing the round-bottom flask in an 80° C. oil bath and stirring for 40 minutes, placing the reactants in the round-bottom flask in a non-pulse type microwave reactor, and starting a microwave reaction in the non-pulse type microwave reactor for 30 minutes to obtain a microwave mixture;

[0102] Step S40, taking the cross-linked mixture and the microwave mixture and placing them in a reactor for mixing, high-speed shear dispersion for 20 minutes, the reactor temperature is 70°C, and the cross-linked mixture and the microwave mixture are centrifuged at a speed of 5000-5500 r / min for 10 minutes to obtain a polyurethane modified acrylic runway surface adhesive.

[0103] Example 3

[0104] An embodiment of the present invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, which includes the following raw materials in parts by weight: 60 parts of aqueous polyurethane emulsion, 45 parts of modified acrylate, 15 parts of modifier, 12 parts of flame retardant, 4 parts of antioxidant, 12 parts of cross-linking agent, 3 parts of auxiliary foaming agent, and 22 parts of white oil.

[0105] In this embodiment, the aqueous polyurethane emulsion includes the following raw materials in weight percentage: polyoxypropylene glycol: 30%; isophorone diisocyanate: 25%; 1,6-hexamethylene diisocyanate: 5%; polyethylene glycol: 30%; stannous oxalate: 5%; bismuth isooctanoate: 5%;

[0106] The modified acrylic ester includes the following raw materials in weight percentage: methyl methacrylate: 30%; maleated rosin glycol acrylate: 5%; isobornyl methacrylate: 15%; 2-amino-1,3-propanediol: 10%; methyltrimethoxysilane: 15%; octamethylcyclotetrasiloxane: 15%; surfactant: 5%; emulsifier: 5%.

[0107] In an embodiment of the present invention, a method for preparing an environmentally friendly high-elastic polyurethane-modified acrylic runway surface adhesive is also provided, such as Figure 1 As shown, the preparation method of the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive specifically includes:

[0108] Step S10, placing the modifier and modified acrylate in a reaction kettle, controlling the reaction temperature to 60-65° C., and stirring at a stirring speed of 200 r / min for 30 min;

[0109] Step S20, adding water-based polyurethane emulsion into the reaction kettle, stirring at 70° C. for 1 h, dropping acetone into the reaction kettle at a rate of one drop every 3-5 seconds, continuing the reaction for 2 h, adding a crosslinking agent into the reaction kettle, stirring and mixing with a stirrer at 500 r / min for 40 min, to obtain a crosslinked mixture;

[0110] Step S30, taking a flame retardant, an antioxidant, an auxiliary foaming agent, and white oil and placing them in a round-bottom flask to mix, and placing the round-bottom flask in an 80° C. oil bath and stirring for 40 minutes, placing the reactants in the round-bottom flask in a non-pulse type microwave reactor, and starting a microwave reaction in the non-pulse type microwave reactor for 30 minutes to obtain a microwave mixture;

[0111] Step S40, taking the cross-linked mixture and the microwave mixture and placing them in a reactor for mixing, high-speed shear dispersion for 20 minutes, the reactor temperature is 70°C, and the cross-linked mixture and the microwave mixture are centrifuged at a speed of 5000-5500 r / min for 10 minutes to obtain a polyurethane modified acrylic runway surface adhesive.

[0112] Example 4

[0113] An embodiment of the present invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, which includes the following raw materials in parts by weight: 100 parts of aqueous polyurethane emulsion, 60 parts of modified acrylate, 30 parts of modifier, 16 parts of flame retardant, 12 parts of antioxidant, 17 parts of cross-linking agent, 9 parts of auxiliary foaming agent, and 28 parts of white oil.

[0114] In this embodiment, the aqueous polyurethane emulsion includes the following raw materials in weight percentage: polyoxypropylene glycol: 30%; isophorone diisocyanate: 25%; 1,6-hexamethylene diisocyanate: 5%; polyethylene glycol: 30%; stannous oxalate: 5%; bismuth isooctanoate: 5%;

[0115] The modified acrylic ester includes the following raw materials in weight percentage: methyl methacrylate: 30%; maleated rosin glycol acrylate: 5%; isobornyl methacrylate: 15%; 2-amino-1,3-propanediol: 10%; methyltrimethoxysilane: 15%; octamethylcyclotetrasiloxane: 15%; surfactant: 5%; emulsifier: 5%.

[0116] In an embodiment of the present invention, a method for preparing an environmentally friendly high-elastic polyurethane-modified acrylic runway surface adhesive is also provided, such as Figure 1 As shown, the preparation method of the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive specifically includes:

[0117] Step S10, placing the modifier and modified acrylate in a reaction kettle, controlling the reaction temperature to 60-65° C., and stirring at a stirring speed of 200 r / min for 30 min;

[0118] Step S20, adding water-based polyurethane emulsion into the reaction kettle, stirring at 70° C. for 1 h, dropping acetone into the reaction kettle at a rate of one drop every 3-5 seconds, continuing the reaction for 2 h, adding a crosslinking agent into the reaction kettle, stirring and mixing with a stirrer at 500 r / min for 40 min, to obtain a crosslinked mixture;

[0119] Step S30, taking a flame retardant, an antioxidant, an auxiliary foaming agent, and white oil and placing them in a round-bottom flask to mix, and placing the round-bottom flask in an 80° C. oil bath and stirring for 40 minutes, placing the reactants in the round-bottom flask in a non-pulse type microwave reactor, and starting a microwave reaction in the non-pulse type microwave reactor for 30 minutes to obtain a microwave mixture;

[0120] Step S40, taking the cross-linked mixture and the microwave mixture and placing them in a reactor for mixing, high-speed shear dispersion for 20 minutes, the reactor temperature is 70°C, and the cross-linked mixture and the microwave mixture are centrifuged at a speed of 5000-5500 r / min for 10 minutes to obtain a polyurethane modified acrylic runway surface adhesive.

[0121] Example 5

[0122] An embodiment of the present invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, which includes the following raw materials in parts by weight: 80 parts of aqueous polyurethane emulsion, 50 parts of modified acrylate, 25 parts of modifier, 14 parts of flame retardant, 10 parts of antioxidant, 15 parts of cross-linking agent, 6 parts of auxiliary foaming agent, and 25 parts of white oil.

[0123] In this embodiment, the aqueous polyurethane emulsion includes the following raw materials in weight percentage: polyoxypropylene glycol: 30%; isophorone diisocyanate: 25%; 1,6-hexamethylene diisocyanate: 5%; polyethylene glycol: 30%; stannous oxalate: 5%; bismuth isooctanoate: 5%;

[0124] The modified acrylic ester includes the following raw materials in weight percentage: methyl methacrylate: 30%; maleated rosin glycol acrylate: 5%; isobornyl methacrylate: 15%; 2-amino-1,3-propanediol: 10%; methyltrimethoxysilane: 15%; octamethylcyclotetrasiloxane: 15%; surfactant: 5%; emulsifier: 5%.

[0125] In an embodiment of the present invention, a method for preparing an environmentally friendly high-elastic polyurethane-modified acrylic runway surface adhesive is also provided, such as Figure 1As shown, the preparation method of the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive specifically includes:

[0126] Step S10, placing the modifier and modified acrylate in a reaction kettle, controlling the reaction temperature to 60-65° C., and stirring at a stirring speed of 200 r / min for 30 min;

[0127] Step S20, adding water-based polyurethane emulsion into the reaction kettle, stirring at 70° C. for 1 h, dropping acetone into the reaction kettle at a rate of one drop every 3-5 seconds, continuing the reaction for 2 h, adding a crosslinking agent into the reaction kettle, stirring and mixing with a stirrer at 500 r / min for 40 min, to obtain a crosslinked mixture;

[0128] Step S30, taking a flame retardant, an antioxidant, an auxiliary foaming agent, and white oil and placing them in a round-bottom flask to mix, and placing the round-bottom flask in an 80° C. oil bath and stirring for 40 minutes, placing the reactants in the round-bottom flask in a non-pulse type microwave reactor, and starting a microwave reaction in the non-pulse type microwave reactor for 30 minutes to obtain a microwave mixture;

[0129] Step S40, taking the cross-linked mixture and the microwave mixture and placing them in a reactor for mixing, high-speed shear dispersion for 20 minutes, the reactor temperature is 70°C, and the cross-linked mixture and the microwave mixture are centrifuged at a speed of 5000-5500 r / min for 10 minutes to obtain a polyurethane modified acrylic runway surface adhesive.

[0130] The embodiment of the present invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, which uses water-based polyurethane emulsion and modified acrylate as base materials. The method of modifying the water-based polyurethane emulsion by modified acrylate is more environmentally friendly, and the hydrophobicity and heat resistance of the runway surface adhesive are also improved. The modifier in the raw material ensures that the runway surface adhesive has high elasticity and cross-linking density. The synergistic cooperation of the modifier and the auxiliary foaming agent not only helps to improve the wear resistance, aging resistance and UV resistance of the plastic runway, but also can significantly improve the foaming effect of the plastic runway, which helps to produce uniform and dense bubbles inside the runway surface adhesive material, avoids the agglomeration of the runway surface adhesive, thereby improving the elasticity and comfort of the plastic runway, and ensuring the environmental performance of the plastic runway.

[0131] like Figure 2 As shown, the preparation method of the aqueous polyurethane emulsion specifically comprises:

[0132] Step S101, adding polyoxypropylene glycol, isophorone diisocyanate, and 1,6-hexamethylene diisocyanate into a three-necked flask, mechanically stirring the polyoxypropylene glycol, isophorone diisocyanate, and 1,6-hexamethylene diisocyanate at a stirring speed of 100-150 r / min, controlling the temperature at 85-92° C., and stirring for 60 minutes;

[0133] It should be noted that polyoxypropylene glycol, isophorone diisocyanate, and 1,6-hexamethylene diisocyanate are all of analytical grade, and polyoxypropylene glycol, isophorone diisocyanate, and 1,6-hexamethylene diisocyanate are purchased from MacLean Reagent Company, and polyethylene glycol, stannous oxalate, and bismuth isooctanoate are all analytical grade products provided by Aladdin Reagent Company.

[0134] Step S102, polyethylene glycol, stannous oxalate, and bismuth isooctanoate are sequentially added into a three-necked flask, the temperature of the three-necked flask is adjusted to 70-75° C., and the mixture is stirred and mixed for 100 minutes;

[0135] Step S103, adding acetone into the three-necked flask to dilute the reactants in the three-necked flask, then adding hydroxypropyl acrylate to cap, keeping the temperature at 70° C. for 60 minutes, cooling the three-necked flask to room temperature, adding deionized water into the three-necked flask and stirring to disperse, then removing the acetone to obtain an aqueous polyurethane emulsion.

[0136] In the embodiment of the present invention, an aqueous polyurethane emulsion and a preparation method thereof are provided. The aqueous polyurethane emulsion uses polyoxypropylene glycol, isophorone diisocyanate, and 1,6-hexamethylene diisocyanate as raw materials, so that the prepared aqueous polyurethane emulsion has lower toxicity and better mechanical properties. The use of stannous oxalate and bismuth isooctanoate as catalysts further ensures that the aqueous polyurethane emulsion has lower toxicity and better hydrolysis resistance stability, while also providing good fluidity and foam openness, which helps to improve the performance of the aqueous polyurethane emulsion.

[0137] The present invention also provides a method for preparing modified acrylate. Figure 3 The schematic diagram of the process flow of the modified acrylate preparation method is shown, and the modified acrylate preparation method specifically includes:

[0138] Step S201, acetone is placed in a four-necked flask, the four-necked flask is placed in a constant temperature water bath, the four-necked flask is vacuumed for 30 minutes at 50° C., methyl methacrylate and lauroyl peroxide are added, stirred and mixed for 20 minutes, and then allowed to stand for 5 minutes;

[0139] Step S202, adding maleic rosin ethylene glycol acrylate into a four-necked flask, stirring the four-necked flask with a magnetic stirrer, controlling the stirring speed to 50-80 r / min, heating the four-necked flask to 60° C., and keeping the temperature for reaction for 60 minutes to obtain an oil phase mixture;

[0140] Step S203, taking a surfactant and mixing it with an equal volume of anhydrous ethanol, using an equal volume of cocamidopropyl betaine and sodium lauryl sulfate to form a surfactant, adding 3 times the volume of deionized water to the surfactant and anhydrous ethanol composite solution to obtain a surfactant dilution, injecting the surfactant dilution into a magnetic stirrer and stirring for 20 minutes, and heating the surfactant dilution to 60° C. with the magnetic stirrer;

[0141] In this embodiment, methyl methacrylate, lauroyl peroxide, and maleated rosin glycol acrylate are all of industrial grade analytical grade provided by Sinopharm Chemical Reagent Co., Ltd., while oleamidopropyl betaine and sodium dodecyl sulfate are of industrial grade analytical grade provided by Shanghai Aladdin Biochemical Co., Ltd., and the magnetic stirrer model can be SZCL-2A type stirrer.

[0142] Step S204, take the surfactant dilution and place it in the oil phase mixture, and install a condenser and a reflux tube in the four-necked flask containing the oil phase mixture, stir and mix the surfactant dilution and the oil phase mixture, heat the four-necked flask to 80°C, keep the temperature for 100 minutes, then heat the four-necked flask to 95°C, keep the temperature for 120 minutes, let it stand for 3 hours after the reaction, wash the reaction product with water, and pass it through a 30-mesh sieve to remove impurities to obtain the first modified component.

[0143] In an embodiment of the present invention, the first modified component is compounded by methyl methacrylate, lauroyl peroxide, cocamidopropyl betaine and sodium lauryl sulfate, thereby obtaining a rosin-based macroporous acrylic resin containing an ester group, thereby achieving modification of the polyurethane, ensuring the hardness, toughness and wear resistance of the polyurethane material, which makes the modified polyacrylate polyurethane composite material show better stability and durability when subjected to external forces.

[0144] Step S205, isobornyl methacrylate, 2-amino-1,3-propanediol, and acetonitrile are placed in a reaction kettle and mixed, nitrogen is introduced into the reaction kettle for protection, the reaction kettle is stirred for reaction, the stirring speed is 100-150 r / min, the reaction kettle temperature is 65-70° C., and the reaction time is 7-8 h to obtain a diol containing isobornyl methacrylate and an amino group;

[0145] It should be noted that isobornyl methacrylate and 2-amino-1,3-propanediol were provided by Shanghai Civic Chemical Technology Co., Ltd., and acetonitrile was provided by Shanghai Titan Technology Co., Ltd. By introducing isobornyl methacrylate into 2-amino-1,3-propanediol, the second modified component has the bio-based hydrophobic properties of isobornyl methacrylate, thereby ensuring the hardness and flexibility of the second modified component.

[0146] Step S206, adding methyltrimethoxysilane and octamethylcyclotetrasiloxane into a reaction container, adding tetradecyltrimethylammonium chloride into the reaction container, the molar ratio of tetradecyltrimethylammonium chloride to the mixture of methyltrimethoxysilane and octamethylcyclotetrasiloxane is 10:1, stirring the reaction container at a speed of 150-200 r / min for 40 minutes, adding ammonia water into the reaction container, and stirring for 10 minutes;

[0147] Step S207, putting a diol containing methacrylic acid isobornyl and amino groups into a reaction container, stirring at room temperature for 50 minutes, to obtain a second modified component;

[0148] Step S208, taking the first modified component and the second modified component and placing them in a reaction kettle, dropping an emulsifier into the reaction kettle, the emulsifier is SE-10 emulsifier, stirring and mixing for 40 minutes, and obtaining modified acrylate.

[0149] In this embodiment, methyltrimethoxysilane and octamethylcyclotetrasiloxane are industrial grade analytical grade provided by Aladdin Reagent Company. Methyltrimethoxysilane and octamethylcyclotetrasiloxane are mixed with a diol containing methacrylate isobornyl and amino groups, and the organosiloxane can be introduced into the first modified component. The low surface energy and good compatibility of the organosiloxane are used to modify the acrylate, thereby further ensuring the strength and stability of the modified acrylate.

[0150] In this embodiment, the modifier includes the following raw materials in weight percentage:

[0151] Coconut oil: 30%;

[0152] Acetic acid: 10%;

[0153] Dibutyltin laurate: 5%;

[0154] Graphene oxide: 30%;

[0155] Polyethyleneimine: 25%;

[0156] It should be noted that the coconut oil was provided by Nantong Runfeng Petrochemical Co., Ltd., acetic acid, dibutyltin laurate, and polyethyleneimine were provided by Sinopharm Chemical Reagent Company, and graphene oxide was provided by Zhongke Carbon Nanotechnology Co., Ltd.

[0157] The present invention also provides a method for preparing the modifier. Figure 4 The schematic diagram of the implementation process of the method for preparing the modifier is shown, and the method for preparing the modifier specifically includes:

[0158] Step S301, taking coconut oil and acetic acid, placing the coconut oil and acetic acid in a three-necked flask, the three-necked flask is equipped with a magnetic stirrer, a condenser, and a reflux tube, placing the three-necked flask in a 50° C. oil bath and heating for 20 minutes, and the stirring speed of the magnetic stirrer is 100-120 r / min;

[0159] Step S302, hydrogen peroxide and concentrated sulfuric acid are added dropwise into a three-necked flask, wherein the mass ratio of coconut oil, hydrogen peroxide, and concentrated sulfuric acid is 1:0.5-0.6:0.002-0.003. After the addition is completed, the temperature of the oil bath is adjusted to 70° C., and the reaction is continued for 8 hours. After the reaction is completed, the reaction is cooled to room temperature, and the water phase in the three-necked flask is separated;

[0160] Step S303, taking equal volumes of methanol and hydrochloric acid into a three-necked flask, the mass ratio of methanol to coconut oil is 0.2:1, condensing and refluxing at 65° C. for 2 h, cooling to room temperature, separating the water phase in the three-necked flask, and obtaining coconut oil polyol;

[0161] Step S304, dibutyltin laurate and coconut oil polyol are placed in a round-bottom flask, nitrogen is introduced into the round-bottom flask for protection, the mixture in the round-bottom flask is stirred, reacted at 65° C. for 30 minutes, and allowed to stand for 30 minutes to obtain a coconut oil polyol mixture for standby use;

[0162] Step S305, taking graphene oxide, adding graphene oxide into a reactor, passing nitrogen into the reactor for protection, adding 10 times the volume of deionized water into the reactor, stirring at 80° C. for 3 h, adding polyethyleneimine into the reactor, stirring at 85° C. for 3 h, cooling the reactor to room temperature, placing the mixture in the reactor in a centrifuge for centrifugation, the speed of the centrifuge is 8000-8500 r / min, and after centrifugation for 30 min, modified graphene is obtained;

[0163] Step S306, taking the modified graphene and the coconut oil polyol mixture and mixing them, stirring at 75° C. for 40 minutes, then heating to 60° C. and ultrasonicating for 35 minutes to obtain a modifier.

[0164] In an embodiment of the present invention, a modifier and a preparation method thereof are provided. The modifier uses coconut oil as a raw material to ensure the flexibility and high elasticity of the modifier. Polyethyleneimine is then used as a modifier to modify graphene oxide, so that the graphene oxide has better dispersibility and matrix compatibility. The modifier acts on waterborne polyurethane, so that the thermal stability, tensile strength and shape memory properties of the waterborne polyurethane are significantly improved.

[0165] The auxiliary foaming agent includes the following raw materials in weight percentage:

[0166] Tetraethyl orthosilicate: 40%;

[0167] Copper sulfate: 20%;

[0168] Hydrazine hydrate: 20%;

[0169] Ammonia water: 10%;

[0170] Ethanol: 10%;

[0171] like Figure 5 As shown, the preparation method of the auxiliary foaming agent specifically comprises:

[0172] Step S401, using tetraethyl orthosilicate as a silicon source and ammonia water as a catalyst, mixing ammonia water and ethanol in a reaction kettle at room temperature, stirring at a stirring speed of 150-200 r / min for 30 min, adding tetraethyl orthosilicate dropwise into the reaction kettle, and continuing to stir for 3 h to obtain a silicon dioxide dispersion;

[0173] In this embodiment, the classic sol-gel method is used to prepare nano-silica during the preparation of the silica dispersion, which ensures the uniformity of the particle size of the silica dispersion, thereby facilitating the combination of the loaded copper ions with the silica dispersion, so that the prepared auxiliary foaming agent helps to produce uniform and dense bubbles inside the material, thereby improving the elasticity and comfort of the plastic track, which not only helps the foaming of the material, but also strengthens the material.

[0174] Step S402, taking a silica dispersion, heating the silica dispersion to 45° C., then adding a copper sulfate solution to the silica dispersion, stirring at 300 r / min for 2 h, and filtering the silica dispersion to obtain a silica filter cake loaded with copper ions;

[0175] Step S403, using hydrazine hydrate as a reducing agent, taking a silica filter cake and placing it in a reactor, dispersing the silica filter cake in 10 times the volume of deionized water, heating to 70° C., adjusting the pH value of the reactor to 10-10.2 with a sodium hydroxide solution, adding hydrazine hydrate to the reactor, reacting for 2 hours, filtering, washing the filter cake with deionized water for 3-5 times, grinding into powder, and obtaining an auxiliary foaming agent.

[0176] In the embodiment of the present invention, the silicon dioxide dispersion is modified by loading copper ions, so that the prepared auxiliary foaming agent can not only ensure the high elasticity of the surface adhesive, but also improve the antibacterial property of the surface adhesive.

[0177] It should be noted that the flame retardant is a mixture of antimony trioxide and expandable graphite, and the mass ratio of antimony trioxide to expandable graphite is 1:2;

[0178] The antioxidant is antioxidant RD, the cross-linking agent is a mixture of maleopimaric acid ethylene glycol acrylate and dicumyl peroxide, and the mass ratio of maleopimaric acid ethylene glycol acrylate to dicumyl peroxide is 1:1.

[0179] Comparative Example 1

[0180] In this comparative example, the raw materials of the environmentally friendly high-elastic polyurethane modified acrylic runway surface glue do not include: modified acrylate, and the other raw materials are the same as those in Example 5, including the following raw materials in parts by weight: 80 parts of aqueous polyurethane emulsion, 20 parts of modifier, 14 parts of flame retardant, 10 parts of antioxidant, 15 parts of cross-linking agent, 6 parts of auxiliary foaming agent, and 25 parts of white oil. The preparation method of modified acrylate is the same as that in Example 5.

[0181] Comparative Example 2

[0182] In this comparative example, the raw materials of the environmentally friendly high-elastic polyurethane modified acrylic runway surface glue do not include: modifier, and the other raw materials are the same as those in Example 5, including the following raw materials in parts by weight: 80 parts of aqueous polyurethane emulsion, 50 parts of modified acrylate, 13 parts of flame retardant, 8 parts of antioxidant, 14 parts of cross-linking agent, 5 parts of auxiliary foaming agent, and 27 parts of white oil. The preparation method of modified acrylate is the same as that in Example 5.

[0183] Comparative Example 3

[0184] In this comparative example, the raw materials of the environmentally friendly high-elastic polyurethane modified acrylic runway surface glue do not include: auxiliary foaming agent, and the other raw materials are the same as those in Example 5, including the following raw materials in parts by weight: 100 parts of aqueous polyurethane emulsion, 60 parts of modified acrylate, 18 parts of modifier, 13 parts of flame retardant, 11 parts of antioxidant, 15 parts of cross-linking agent, and 25 parts of white oil. The preparation method of modified acrylate is the same as that in Example 5.

[0185] Comparative Example 4

[0186] In this comparative example, the raw materials of the environmentally friendly high-elastic polyurethane modified acrylic runway surface glue do not include: modifier, auxiliary foaming agent, and other raw materials are the same as those in Example 5, including the following raw materials in parts by weight: 90 parts of aqueous polyurethane emulsion, 55 parts of modified acrylate, 13 parts of flame retardant, 11 parts of antioxidant, 15 parts of cross-linking agent, and 23 parts of white oil. The preparation method of modified acrylate is the same as that in Example 5.

[0187] Comparative Example 5

[0188] In this comparative example, the raw materials of the environmentally friendly high-elastic polyurethane modified acrylic runway surface glue do not include: modified acrylate, modifier, auxiliary foaming agent, and other raw materials are the same as those in Example 5, including the following raw materials in parts by weight: 90 parts of aqueous polyurethane emulsion, 12 parts of flame retardant, 8 parts of antioxidant, 15 parts of cross-linking agent, and 26 parts of white oil. The preparation method of modified acrylate is the same as that in Example 5.

[0189] Performance Testing:

[0190] The runway surface rubbers prepared in Examples 1-5 and Comparative Examples 1-5 of the present invention were used to prepare an environmentally friendly high-elastic polyurethane modified acrylic runway, and a test was performed on the runway surface rubbers. The specific test examples are as follows:

[0191] The tensile strength and elongation at break of the products obtained in Examples 1-5 and Comparative Examples 1-5 were tested using an XLW-500 electronic tensile tester (Jinan Languang Electromechanical Technology Co., Ltd.) at a tensile rate of 150 mm / min. The test results are shown in Table 1. Figure 6 , Figure 7 As shown, Figure 6 The tensile strength test results of Examples 1-5 and Comparative Examples 1-5 of the present invention are shown. Figure 7 The test results of elongation at break of inventive examples 1-5 and comparative examples 1-5 are shown.

[0192] Table 1

[0193]

[0194] It can be concluded from Table 1 that the products prepared in Examples 1-5 of the present invention have higher tensile strength and elongation at break than those in Comparative Examples 1-5. It can be seen that the modified acrylate, modifier and auxiliary foaming agent in the raw materials of the track surface rubber in the embodiments of the present invention have obvious performance improvements on the tensile strength and elasticity of the track.

[0195] Take the products obtained in Examples 1-5 and Comparative Examples 4-5, and two groups of commercially available polyurethane products (commercially available product 1 and commercially available product 2), cut a sheet substrate with a specification of 1×1 cm, place it under natural ventilation at room temperature (25°C) for 7 days, put it in a 50°C oven to dry for 2 days, take it out, soak the substrate in anhydrous ethanol, put the substrate into a small plate combustion test equipment for testing, and measure the diameter of the combustion plaque on the surface of the substrate after combustion. The test results are shown in Table 2 and Figure 8 , the flame retardancy test results are shown.

[0196] Table 2

[0197]

[0198] As can be seen from Table 2, compared with commercially available products 1 and 2, and comparative examples 4-5, the flame retardancy and flame retardancy of the products prepared in Examples 1-5 of the present invention are improved. It can be seen that the flame retardant and the modifier in the raw materials cooperate with each other to achieve the modification of the flame retardant and the aqueous polyurethane emulsion, which ensures the strength and high elasticity of the product while also making the product have higher flame retardancy.

[0199] The products obtained in Examples 1-5 and Comparative Examples 4-5, and two groups of commercially available polyurethane products (Commercially Available Product 1, Commercially Available Product 2) were taken and thermogravimetric analysis was performed using a TG-209F1-Libra thermogravimeter. 100 mg of the products obtained in Examples 1-5 and Comparative Examples 4-5, and two groups of commercially available polyurethane products (Commercially Available Product 1, Commercially Available Product 2) were heated from 40°C to 600°C at a rate of 15°C / min in a nitrogen atmosphere to test the 5% weight loss temperature of the products obtained in Examples 1-5 and Comparative Examples 4-5, and two groups of commercially available polyurethane products (Commercially Available Product 1, Commercially Available Product 2). The test results are shown in Table 3. Fig. 9 , the thermogravimetric analysis test results are shown.

[0200] Table 3

[0201]

[0202] As can be seen from Table 3, the 5% weight loss temperature of Examples 1-5 of the present invention is significantly improved compared with the products prepared in Comparative Examples 4-5 and the two groups of commercial polyurethane products (commercial product 1 and commercial product 2), indicating that the products prepared in Examples 1-5 of the present invention have higher thermal stability. Therefore, it can be seen that a strong interfacial interaction is generated between the modifier, the aqueous polyurethane emulsion, and the modified acrylate, and this interaction is an important reason for the improvement of thermal stability. Thus, the thermal stability of the product is improved.

[0203] In summary, the present invention provides an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive and a preparation method thereof. An environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive is provided in an embodiment of the present invention. The aqueous polyurethane emulsion and modified acrylate are used as base materials. The method of modifying the aqueous polyurethane emulsion by modified acrylate is more environmentally friendly, and the hydrophobicity and heat resistance of the runway surface adhesive are also improved. The modifier in the raw material ensures that the runway surface adhesive has high elasticity and cross-linking density. The synergistic combination of the modifier and the auxiliary foaming agent not only helps to improve the wear resistance, aging resistance and UV resistance of the plastic runway, but also can significantly improve the foaming effect of the plastic runway, which helps to produce uniform and dense bubbles inside the runway surface adhesive material, avoids agglomeration of the runway surface adhesive, thereby improving the elasticity and comfort of the plastic runway, and ensuring the environmental performance of the plastic runway.

[0204] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the scope of protection of the invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on these embodiments, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in this field can still combine, add, delete or make other adjustments to the features in the various embodiments of the present invention according to the circumstances without conflict, without making creative work, so as to obtain different other technical solutions that do not deviate from the concept of the present invention in essence, and these technical solutions also belong to the scope of protection of the present invention.

Claims

1. An environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, characterized in that: The environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive comprises the following raw materials in parts by weight: 50-110 parts of waterborne polyurethane emulsion, 40-65 parts of modified acrylate, 10-40 parts of modifier, 10-18 parts of flame retardant, 1-15 parts of antioxidant, 10-20 parts of cross-linking agent, 1-10 parts of auxiliary foaming agent, and 20-30 parts of white oil; The modified acrylate comprises the following raw materials in weight percentage: Methyl methacrylate: 30%; Maleic rosin glycol acrylate: 5%; Isobornyl methacrylate: 15%; 2-Amino-1,3-propanediol: 10%; Methyltrimethoxysilane: 15%; Octamethylcyclotetrasiloxane: 15%; Surfactant: 5%; Emulsifier: 5%; The modifier comprises the following raw materials in weight percentage: Coconut oil: 30%; Acetic acid: 10%; Dibutyltin laurate: 5%; Graphene oxide: 30%; Polyethyleneimine: 25%; The auxiliary foaming agent includes the following raw materials in weight percentage: Ethyl orthosilicate: 40%; Copper sulfate: 20%; Hydrazine hydrate: 20%; Ammonia water: 10%; Ethanol: 10%; The aqueous polyurethane emulsion comprises the following raw materials in percentage by weight: Polyoxypropylene glycol: 30%; Isophorone diisocyanate: 25%; 1,6-hexamethylene diisocyanate: 5%; Polyethylene glycol: 30%; Stannous oxalate: 5%; Bismuth isooctanoate: 5%; The preparation method of the aqueous polyurethane emulsion specifically comprises: Add polyoxypropylene glycol, isophorone diisocyanate and 1,6-hexamethylene diisocyanate into a three-necked flask, mechanically stir the polyoxypropylene glycol, isophorone diisocyanate and 1,6-hexamethylene diisocyanate at a stirring speed of 100-150 r / min, control the temperature at 85-92°C, and stir for 60 minutes; Add polyethylene glycol, stannous oxalate and bismuth isooctanoate into a three-necked flask in sequence, adjust the temperature of the three-necked flask to 70-75° C., and stir and mix for 100 minutes; Acetone was added into the three-necked flask to dilute the reactants in the three-necked flask, and then hydroxypropyl acrylate was added for end-capping. The reaction was kept at 70° C. for 60 minutes. The three-necked flask was cooled to room temperature, deionized water was added into the three-necked flask and stirred to disperse, and then the acetone was removed to obtain a waterborne polyurethane emulsion.

2. The environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive according to claim 1, characterized in that: The environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive includes the following raw materials in parts by weight: 60-100 parts of aqueous polyurethane emulsion, 45-60 parts of modified acrylate, 15-30 parts of modifier, 12-16 parts of flame retardant, 4-12 parts of antioxidant, 12-17 parts of cross-linking agent, 3-9 parts of auxiliary foaming agent and 22-28 parts of white oil.

3. The environmentally friendly high-elastic polyurethane modified acrylic runway surface rubber according to claim 1, characterized in that: The preparation method of the modified acrylate specifically comprises: Acetone was placed in a four-necked flask, which was placed in a constant temperature water bath. The four-necked flask was vacuumed for 30 minutes at 50°C, methyl methacrylate and lauroyl peroxide were added, stirred and mixed for 20 minutes, and then allowed to stand for 5 minutes. Add maleic rosin ethylene glycol acrylate into a four-necked flask, stir the four-necked flask with a magnetic stirrer, and control the stirring speed to 50-80 r / min. Heat the four-necked flask to 60° C. and keep the temperature for 60 minutes to obtain an oil phase mixture; The surfactant was compounded with an equal volume of anhydrous ethanol, and an equal volume of cocamidopropyl betaine and sodium lauryl sulfate was used to form a surfactant. Three times the volume of deionized water was added to the surfactant and anhydrous ethanol compound solution to obtain a surfactant dilution. The surfactant dilution was injected into a magnetic stirrer and stirred for 20 minutes. The magnetic stirrer heated the surfactant dilution to 60°C. The surfactant dilution is placed in the oil phase mixture, and a condenser and a reflux tube are installed in the four-necked flask containing the oil phase mixture, and the surfactant dilution and the oil phase mixture are stirred and mixed, and the four-necked flask is heated to 80° C. and kept warm for 100 minutes, and then the four-necked flask is heated to 95° C. and kept warm for 120 minutes. After the reaction, the reaction is allowed to stand for 3 hours, and the reaction product is washed with water and passed through a 30-mesh sieve plate to remove impurities to obtain a first modified component; Isobornyl methacrylate, 2-amino-1,3-propanediol and acetonitrile are placed in a reaction kettle and mixed, nitrogen is introduced into the reaction kettle for protection, the reaction kettle is stirred for reaction, the stirring speed is 100-150r / min, the reaction kettle temperature is 65-70°C, the reaction time is 7-8h, and a diol containing isobornyl methacrylate and an amino group is obtained; Add methyltrimethoxysilane and octamethylcyclotetrasiloxane into a reaction container, add tetradecyltrimethylammonium chloride into the reaction container, stir the reaction container at a speed of 150-200 r / min for 40 minutes, add ammonia water into the reaction container, and stir for 10 minutes; Putting a diol containing methacrylic acid isobornyl and amino groups into a reaction container, stirring at room temperature for 50 minutes, to obtain a second modified component; The first modified component and the second modified component were placed in a reaction kettle, and an emulsifier was added dropwise to the reaction kettle. The emulsifier was SE-10 emulsifier, and the mixture was stirred for 40 minutes to obtain modified acrylate.

4. The environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive as claimed in claim 3, characterized in that: The preparation method of the modifier specifically comprises: Take coconut oil and acetic acid, put them in a three-necked flask, the three-necked flask is equipped with a magnetic stirrer, a condenser, and a reflux tube, put the three-necked flask in a 50°C oil bath and heat it for 20 minutes, and the stirring speed of the magnetic stirrer is 100-120r / min; Hydrogen peroxide and concentrated sulfuric acid were added dropwise into a three-necked flask, with the mass ratio of coconut oil, hydrogen peroxide and concentrated sulfuric acid being 1:0.5-0.6:0.002-0.

003. After the addition was completed, the temperature of the oil bath was adjusted to 70°C, and the reaction was continued for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the aqueous phase in the three-necked flask was separated; Take equal volumes of methanol and hydrochloric acid and place them in a three-necked flask, the mass ratio of methanol to coconut oil is 0.2:1, condense and reflux for reaction at 65°C for 2h, cool to room temperature, separate the water phase in the three-necked flask, and obtain coconut oil polyol; Place dibutyltin laurate and coconut oil polyol in a round-bottom flask, introduce nitrogen into the round-bottom flask for protection, stir the mixture in the round-bottom flask, react at 65° C. for 30 minutes, and stand for 30 minutes to obtain a coconut oil polyol mixture for standby use; Take graphene oxide, add graphene oxide into a reactor, pass nitrogen into the reactor for protection, add 10 times the volume of deionized water into the reactor, stir at 80° C. for 3 h, add polyethyleneimine into the reactor, stir at 85° C. for 3 h, cool the reactor to room temperature, place the mixture in the reactor in a centrifuge for centrifugation, the speed of the centrifuge is 8000-8500 r / min, and after centrifugation for 30 min, obtain modified graphene; The modified graphene was mixed with a coconut oil polyol mixture, stirred at 75° C. for 40 min, then heated to 60° C. and ultrasonicated for 35 min to obtain a modifier.

5. The environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive as claimed in claim 4, characterized in that: The preparation method of the auxiliary foaming agent specifically comprises: Using tetraethyl orthosilicate as a silicon source and ammonia water as a catalyst, ammonia water and ethanol are placed in a reaction kettle and mixed at room temperature, stirred at a stirring speed of 150-200 r / min for 30 minutes, tetraethyl orthosilicate is added dropwise to the reaction kettle, and stirring is continued for 3 hours to obtain a silicon dioxide dispersion; Taking a silica dispersion, heating the silica dispersion to 45° C., then adding a copper sulfate solution to the silica dispersion, stirring at 300 r / min for 2 h, and filtering the silica dispersion to obtain a silica filter cake loaded with copper ions; With hydrazine hydrate as a reducing agent, a silica filter cake is placed in a reaction kettle, the silica filter cake is dispersed in 10 times the volume of deionized water, heated to 70°C, a sodium hydroxide solution is used to adjust the pH value of the reaction kettle to 10-10.2, hydrazine hydrate is added to the reaction kettle, reacted for 2 hours, filtered, the filter cake is washed with deionized water for 3-5 times, ground into powder, and an auxiliary foaming agent is obtained.

6. The environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive according to claim 1, characterized in that: The flame retardant is a mixture of antimony trioxide and expandable graphite, and the mass ratio of antimony trioxide to expandable graphite is 1:2; The antioxidant is antioxidant RD, the cross-linking agent is a mixture of maleopimaric acid ethylene glycol acrylate and dicumyl peroxide, and the mass ratio of maleopimaric acid ethylene glycol acrylate to dicumyl peroxide is 1:

1.

7. A method for preparing an environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive, used for preparing the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive as claimed in any one of claims 1 to 6, characterized in that: The method for preparing the environmentally friendly high-elastic polyurethane modified acrylic runway surface adhesive specifically comprises: Place the modifier and modified acrylate in a reaction kettle, control the reaction temperature to 60-65°C, and stir at a stirring speed of 200 r / min for 30 min; Add waterborne polyurethane emulsion into the reactor, stir at 70°C for 1 hour, drop acetone into the reactor at a rate of one drop every 3-5 seconds, continue the reaction for 2 hours, add crosslinking agent into the reactor, stir and mix with a stirrer at 500 r / min for 40 minutes to obtain a crosslinked mixture; The flame retardant, antioxidant, auxiliary foaming agent and white oil were placed in a round-bottom flask for mixing, and the round-bottom flask was placed in an 80°C oil bath for stirring for 40 minutes. The reactants in the round-bottom flask were placed in a non-pulse type microwave reactor, and the non-pulse type microwave reactor was started for microwave reaction for 30 minutes to obtain a microwave mixture; The cross-linked mixture and the microwave mixture were placed in a reactor for mixing and dispersed at high speed for 20 minutes. The temperature of the reactor was 70° C. The cross-linked mixture and the microwave mixture were centrifuged at a speed of 5000-5500 r / min for 10 minutes to obtain a polyurethane modified acrylic runway surface adhesive.

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