阅读说明：本技术 一种抗剥落的环保型彩色防滑路面及其制备方法 (Anti-stripping environment-friendly colorful anti-skid pavement and preparation method thereof ) 是由 穆建青 蔡丽娜 原国华 邓皇根 牟丹 李文光 谢邦柱 王敬 郭东红 郝文斌 高晋 于 2020-12-31 设计创作，主要内容包括：本发明公开了一种抗剥落的环保型彩色防滑路面及其制备方法。所述方法为：首先修补清扫路面；然后摊铺环保型彩色防滑路面胶粘剂,在胶粘剂上撒布彩色陶瓷颗粒；待胶粘剂固化后,喷涂环保型彩色防滑路面面层保护剂。所述的环保型彩色防滑路面胶粘剂是经过聚氨酯增韧改性的,断裂伸长率和抗剪切强度具有较好的匹配性,铺设的彩色防滑路面抗裂性能和耐疲劳性能有了显著提升。面层保护剂的使用有效地提升了彩色防滑路面陶瓷颗粒的抗剥落能力,也进一步提升了环保型彩色防滑路面的抗水损能力。相比于常规的彩色防滑路面及水性环氧树脂彩色防滑路面,本发明在环保性能、抗裂性能及耐久性能方面更优异。(The invention discloses an anti-stripping environment-friendly colorful anti-skid pavement and a preparation method thereof. The method comprises the following steps: firstly, repairing and cleaning a road surface; then paving an environment-friendly color anti-skid pavement adhesive, and spreading color ceramic particles on the adhesive; after the adhesive is solidified, the environmental-friendly color antiskid pavement surface layer protective agent is sprayed. The environment-friendly color anti-skid pavement adhesive is toughened and modified by polyurethane, has better matching property of elongation at break and shear strength, and obviously improves the crack resistance and fatigue resistance of the laid color anti-skid pavement. The use of the surface layer protective agent effectively improves the anti-stripping capability of the ceramic particles of the colored anti-skid pavement and further improves the water loss resistance of the environment-friendly colored anti-skid pavement. Compared with the conventional colored anti-skid pavement and the waterborne epoxy resin colored anti-skid pavement, the colored anti-skid pavement has more excellent environmental protection performance, crack resistance and durability.)

1. The preparation method of the anti-stripping environment-friendly colorful anti-skid pavement is characterized by comprising the following specific steps:

1) cleaning and sweeping the constructed pavement, wherein the constructed ground needs to be clean, free of oil stain, pulverization, clear water and floating ash; repairing the damaged part of the base surface by using epoxy mortar, wherein the surface of the concrete needs to be clean, dry and firm;

2) mixing 100 parts by mass of an environment-friendly color anti-skid pavement adhesive A component, 150 parts by mass of an environment-friendly color anti-skid pavement adhesive B component, 100 parts by mass of tap water and 10 parts by mass of pigment, stirring at the rotating speed of 1000 plus 1500rpm for 3-5min, pouring the mixture on a construction pavement, spreading the mixture, and spreading color ceramic particles with the particle size of 1-3mm until the color ceramic particles completely cover the environment-friendly color anti-skid pavement adhesive; curing for more than 24 hours, cleaning the color ceramic particles which are not completely bonded on the surface by using a broom, and blowing by using a road surface blowing tool;

3) uniformly mixing the component A of the environment-friendly color antiskid pavement surface layer protective agent and the component B of the environment-friendly color antiskid pavement surface layer protective agent according to the mass ratio of 1.2-1.5:2, spraying the mixture on the surface of a pavement, and obtaining the anti-stripping environment-friendly color antiskid pavement after the mixture is completely dried.

2. The preparation method according to claim 1, wherein the component A of the environment-friendly color anti-skid pavement adhesive is prepared by the following steps:

1) drying oleum ricini, polyethylene glycol 2000, dimethyl carbonate, and 4,4' -dicyclohexylmethane diisocyanate in vacuum oven at 40 deg.C to remove water, and placing in CaCl₂The dryer (2) is placed for 72 hours at the temperature of 25 ℃;

2) dissolving a mixture of castor oil 10 parts by mole and polyethylene glycol 2000 10 parts by mole in dimethyl carbonate 30 parts by mole, stirring at 45 deg.C until completely dissolved, and adding N₂Heating to 70 ℃ under protection, mechanically stirring at 3000rpm for 3h, N₂A condensation recovery device with the temperature of 5 ℃ is arranged at an outlet and is used for collecting the evaporated dimethyl carbonate;

3) weighing 20 parts by molar weight of 4,4 '-dicyclohexylmethane diisocyanate, slowly dropwise adding the 4,4' -dicyclohexylmethane diisocyanate into the reaction mixture obtained in the step 2), keeping the reaction conditions unchanged after dropwise adding, and continuously reacting for 3 hours to obtain a reaction product I;

4) weighing 15 parts of hydrogenated bisphenol A epoxy resin or hexahydrophthalic acid diglycidyl ester, placing the hydrogenated bisphenol A epoxy resin or hexahydrophthalic acid diglycidyl ester into a reactor, adding boron trifluoride diethyl etherate under the conditions of nitrogen protection, reaction temperature of 70 ℃ and stirring speed of 1500rpm, wherein the addition amount of the boron trifluoride diethyl etherate is 0.5 wt% of the hydrogenated bisphenol A epoxy resin or hexahydrophthalic acid diglycidyl ester, stirring uniformly, slowly dropwise adding a reaction product I for 3 hours, and continuously stirring for reaction for 2 hours after dropwise adding to obtain a reaction product II;

5) heating the reaction product to 80 ℃ and stopping introducing N₂In N at₂A 5 ℃ condensation recovery device at an outlet is connected with a vacuum pump, and the vacuum pump is used for carrying out vacuum pumping treatment at a constant temperature and a constant speed at a stirring speed of 3000rpm until no bubbles are generated to obtain a light yellow transparent viscous liquid substance as a reaction product (c);

6) adding 85 parts of bisphenol A epoxy resin E51 into the reaction product III, adjusting the reaction temperature to 60 ℃, adjusting the stirring speed to 3000rpm, removing the vacuumizing device, communicating the whole reaction equipment with the atmosphere, slowly dripping deionized water for 30min-2h, keeping the temperature and the stirring speed after dripping, and continuously reacting for 30min to obtain a modified epoxy resin emulsion with the solid content of 50 wt%;

7) and (3) adding a stabilizer and a flatting agent with the mass fraction of 0.5 percent into the modified epoxy resin emulsion obtained in the step 6), and continuing stirring for 15min to obtain homogeneous milky emulsion, namely the component A of the environment-friendly color anti-skid pavement adhesive.

3. The preparation method according to claim 1, wherein the preparation step of the B component of the environment-friendly color anti-skid pavement adhesive comprises the following steps:

1) weighing 70 parts by mole of methylcyclopentanediamine and 10 parts by mole of polyetheramine, heating to 60 ℃, stirring and mixing uniformly, and introducing nitrogen for protection;

2) slowly dripping 80 parts of tetrahydrophthalic acid diglycidyl ester with the molar weight into the reactor in the step 1), and continuing to stir at 60 ℃ for 12 hours at the stirring speed of 1500rpm until the mixture becomes brown yellow viscous liquid;

3) slowly dripping 20 parts of hexanediol diglycidyl ether with the molar weight into the product obtained in the step 2), and continuing to stir at 60 ℃ for 8 hours at the stirring speed of 1500rpm after finishing dripping;

4) keeping the temperature and the rotating speed unchanged, slowly dripping deionized water into the product obtained in the step 3) to prepare brown yellow homogeneous liquid with the solid content of 50 wt%, and continuously stirring until no foaming and no wire drawing phenomenon are caused after the dripping is finished, thus obtaining the component B of the environment-friendly color anti-skid pavement adhesive.

4. The preparation method according to claim 1, wherein the preparation of the component A of the environment-friendly color antiskid pavement surface layer protective agent comprises the following steps:

1) drying oleum ricini, trimethylolpropane, dimethyl carbonate, HMDI, hydroxyethyl methacrylate and bis-hydroxymethyl butyric acid in vacuum oven at 40 deg.C to remove water, and placing in CaCl₂The dryer (2) is placed for 72 hours at the temperature of 25 ℃;

2) putting 60 parts of HMDI (high molecular weight polyethylene) in a reactor, adjusting the reaction temperature to 70-75 ℃, stirring at 1500rpm, and introducing N₂Protection, N₂A condensation recovery device with the temperature of 5 ℃ is arranged at an outlet, then a dimethyl carbonate solution in which 3 parts by mole of trimethylolpropane and 7 parts by mole of castor oil are dissolved is slowly dripped, and the reaction is continued for 1 hour after the dripping is finished;

3) adjusting the reaction temperature to 60 ℃, dropwise adding 18 parts of hydroxyethyl methacrylate into the reactor in the step 2), wherein the dropwise adding time is 1h, and the stirring speed is 3000 rpm;

4) further reducing the reaction temperature to 40 ℃, keeping the stirring speed unchanged, adding potassium persulfate into the product obtained in the step 3), slowly dropwise adding 54 parts of MMA monomer in a molar amount for 1h, and rapidly adding phenol after the dropwise adding is completed, wherein the addition amount of the phenol is 0.5% of the mass of the MMA;

5) adjusting the stirring speed to 3000rpm, adjusting the reaction temperature to 60 ℃, dropwise adding 8 parts by mole of bis (hydroxymethyl) butyric acid into the product obtained in the step 4), continuing to react for 1h after dropwise adding is finished, then adding 8 parts by mole of triethylamine at one time, stirring for 30min, and removing the redundant dimethyl carbonate solvent in the reactant by a vacuum-pumping heating mode until no bubbles are generated in the viscous liquid;

6) deionized water is added to adjust the solid content to be 50 wt%, and the mixture is stirred uniformly after a defoaming agent is added, so that the component A of the environment-friendly color pavement surface layer protective agent is obtained.

5. The preparation method of claim 1, wherein the step of preparing the component B of the environment-friendly color pavement surface protective agent comprises the following steps:

1) placing 40 parts by molar weight of hexahydrophthalic acid diglycidyl ester into a reactor, adjusting the reaction temperature to 60 ℃, stirring at 1500rpm, introducing nitrogen for protection, and dropwise adding 15 parts by molar weight of polyetheramine D400 to obtain an epoxy resin prepolymer;

2) weighing 50 parts of castor oil by molar weight, adding boron trifluoride diethyl etherate, wherein the mass of the boron trifluoride diethyl etherate is 0.5 percent of that of the castor oil, uniformly stirring, adjusting the reaction temperature to 60 ℃, introducing nitrogen for protection, and adjusting the stirring speed to 1500 rpm;

3) slowly dripping the epoxy resin prepolymer prepared in the step 1) into the mixture in the step 2), wherein the dripping time is 2h, stirring and reacting for 6h at 60 ℃, the stirring speed is 1500rpm, and dripping DMC to adjust the viscosity of the product;

4) keeping the reaction temperature and the stirring speed unchanged, dropwise adding 20 parts of HMDI (dimethyl formamide) subjected to DMPA (dimethyl formamide) grafting modification into the product obtained in the step 3), and continuing to react for 1h after the dropwise addition is finished;

5) keeping the temperature and the rotating speed unchanged, adding 20 parts by mole of triethanolamine to neutralize the product obtained in the step 4), vacuumizing to remove redundant DMC until no bubbles are generated in the reactant liquid, slowly dropwise adding deionized water to prepare a dispersion liquid with the solid content of 50 wt%, and continuously stirring after dropwise adding until no foaming or wire drawing phenomenon occurs, thus obtaining the component B of the environment-friendly color pavement surface layer protective agent.

Technical Field

The invention belongs to the technical field of pavement maintenance, and particularly relates to an anti-stripping environment-friendly color anti-skid pavement and a preparation method thereof.

Background

The current color antiskid pavement is mainly divided into three categories, namely an epoxy-based color antiskid pavement, a polyurethane-based color antiskid pavement and an MMA-type color antiskid pavement. The epoxy group colored antiskid pavement has high bonding strength and long service life, but is easy to crack due to large stress; the polyurethane-based colored anti-skid pavement has low polyurethane bonding strength, large elongation at break and lower bonding property with a base material than epoxy resin, so that the problems of early-stage ceramsite falling off and middle-and-later-stage light panels are easily caused; compared with a polyurethane-based colored anti-slip pavement, the MMA-type colored anti-slip pavement has the advantages that the performance is greatly improved, the wear resistance and the bonding strength of MMA are improved, but MMA is high in free radical polymerization reaction speed and poor in controllability, ceramic particles cannot be completely immersed into MMA base glue, and the problem of falling and hanging of the MMA due to incomplete bonding is solved. In addition, the traditional color antiskid pavement mostly adopts an oily adhesive, in order to ensure that the adhesive has good fluidity, a great amount of organic solvents and diluents are adopted in the using process, so that a great amount of unstructured VOCs are discharged in the construction process, and along with the gradual development of road construction in the directions of environmental protection, conservation, energy conservation, long service life, functionalization and the like, in the road construction of important components of the capital construction industry, the new technical material which is energy-saving, environment-friendly, excellent in performance, cost reduction and efficiency improvement becomes a new trend and trend of industry development.

The epoxy-based colored anti-skid pavement in the existing colored anti-skid pavement is easy to crack due to overlarge tensile strength of epoxy resin and poor matching with the stress of the pavement, the early grain falling is easy to be serious due to serious and insufficient bonding strength of the traditional polyurethane-based pavement, and the problem that ceramic grains can not be completely sunk into an adhesive and the ceramic grains are easy to fall off due to the fact that the free radical polymerization reaction speed of MMA is too high by adopting a traditional construction method is solved. Therefore, the environment-friendly color antiskid pavement which is energy-saving and environment-friendly, convenient and quick to construct, moderate in bonding strength and elongation at break, capable of effectively preventing ceramic particles from falling off too early and applicable to the current asphalt pavement situation of China has important practical significance.

Disclosure of Invention

The method aims to effectively solve the problems that the existing waterborne epoxy resin has large shrinkage and insufficient elongation at break to cause cracking of the colorful antiskid pavement and the early grain falling seriously causes insufficient abrasion performance of the colorful antiskid pavement. The invention develops an anti-stripping environment-friendly color anti-skid pavement and a preparation method thereof.

The preparation method of the anti-stripping environment-friendly color anti-skid pavement comprises the following steps:

1) cleaning and sweeping the constructed pavement, wherein the constructed ground needs to be clean, free of oil stain, pulverization, clear water and floating ash; repairing the damaged part of the base surface by using epoxy mortar, wherein the surface of the concrete needs to be clean, dry and firm;

2) mixing 100 parts by mass of an environment-friendly color anti-skid pavement adhesive A component, 150 parts by mass of an environment-friendly color anti-skid pavement adhesive B component, 100 parts by mass of tap water and 10 parts by mass of pigment, stirring at the rotating speed of 1000 plus 1500rpm for 3-5min, pouring the mixture on a construction pavement, spreading the mixture, and spreading color ceramic particles with the particle size of 1-3mm until the color ceramic particles completely cover the environment-friendly color anti-skid pavement adhesive; curing for more than 24 hours, cleaning the color ceramic particles which are not completely bonded on the surface by using a broom, and blowing by using a road surface blowing tool;

3) uniformly mixing the component A of the environment-friendly color antiskid pavement surface layer protective agent and the component B of the environment-friendly color antiskid pavement surface layer protective agent according to the mass ratio of 1.2-1.5:2, spraying the mixture on the surface of a pavement, and obtaining the anti-stripping environment-friendly color antiskid pavement after the mixture is dried.

The preparation method of the component A of the environment-friendly color anti-skid pavement adhesive comprises the following steps:

1) drying oleum ricini, polyethylene glycol 2000, dimethyl carbonate, and 4,4' -dicyclohexylmethane diisocyanate in vacuum oven at 40 deg.C to remove water, and placing in CaCl₂The obtained product is placed in a dryer at 25 ℃ for 72 hours;

2) dissolving a mixture of castor oil 10 parts by mole and polyethylene glycol 2000 10 parts by mole in dimethyl carbonate 30 parts by mole, stirring at 45 deg.C until completely dissolved, and adding N₂Heating to 70 ℃ under protection, mechanically stirring at 3000rpm for 3h, N₂A condensation recovery device with the temperature of 5 ℃ is arranged at an outlet and is used for collecting the evaporated dimethyl carbonate;

3) weighing 20 parts by molar weight of 4,4 '-dicyclohexylmethane diisocyanate, slowly dropwise adding the 4,4' -dicyclohexylmethane diisocyanate into the reaction mixture obtained in the step 2), keeping the reaction conditions unchanged after dropwise adding, and continuously reacting for 3 hours to obtain a reaction product I;

4) weighing 15 parts of hydrogenated bisphenol A epoxy resin or hexahydrophthalic acid diglycidyl ester, placing the hydrogenated bisphenol A epoxy resin or hexahydrophthalic acid diglycidyl ester into a reactor, adding boron trifluoride diethyl etherate under the conditions of nitrogen protection, reaction temperature of 70 ℃ and stirring speed of 1500rpm, wherein the addition amount of the boron trifluoride diethyl etherate is 0.5 wt% of the hydrogenated bisphenol A epoxy resin or hexahydrophthalic acid diglycidyl ester, stirring uniformly, slowly dropwise adding a reaction product I for 3 hours, and continuously stirring for reaction for 2 hours after dropwise adding to obtain a reaction product II;

5) heating the reaction product to 80 ℃ and stopping introducing N₂In N at₂A 5 ℃ condensation recovery device at an outlet is connected with a vacuum pump, and the vacuum pump is vacuumized at constant temperature and constant speed at the stirring speed of 3000rpm until no bubbles are generated to obtain a light yellow transparent viscous substance as a reaction product (c);

6) adding 85 parts of bisphenol A epoxy resin E51 into the reaction product III, adjusting the reaction temperature to 60 ℃, adjusting the stirring speed to 3000rpm, removing the vacuumizing device, communicating the whole reaction equipment with the atmosphere, slowly adding deionized water dropwise for 30min-2h, keeping the temperature and the stirring speed after dropwise addition, and continuing to react for 30min to obtain a modified epoxy resin emulsion with the solid content of 50 wt%;

7) and (3) adding a stabilizer and a flatting agent with the mass fraction of 0.5 percent into the modified epoxy resin emulsion obtained in the step 6), and continuing stirring for 15min to obtain homogeneous milky emulsion, namely the component A of the environment-friendly color anti-skid pavement adhesive.

The preparation method of the component B of the environment-friendly color anti-skid pavement adhesive comprises the following steps:

1) weighing 70 parts by mole of methylcyclopentanediamine and 10 parts by mole of polyetheramine, heating to 60 ℃, stirring and mixing uniformly, and introducing nitrogen for protection;

2) slowly dropwise adding 80 parts by molar weight of tetrahydrophthalic acid diglycidyl ester into the reactor in the step 1), and continuously stirring at 60 ℃ for 12 hours at the stirring speed of 1500rpm until the mixture becomes brown yellow viscous liquid;

3) slowly dropwise adding 20 parts by mole of hexanediol diglycidyl ether into the product obtained in the step 2), and continuously stirring at 60 ℃ for 8 hours at the stirring speed of 1500rpm after dropwise adding;

4) keeping the temperature and the rotating speed unchanged, slowly dripping deionized water into the product obtained in the step 3) to prepare brownish yellow homogeneous liquid with the solid content of 50 wt%, and continuously stirring until no foaming and no wire drawing phenomenon are generated after the dripping is finished, thus obtaining the component B of the environment-friendly color anti-skid pavement adhesive.

The preparation method of the component A of the environment-friendly color antiskid pavement surface layer protective agent comprises the following steps:

1) drying oleum ricini, trimethylolpropane, dimethyl carbonate, HMDI, hydroxyethyl methacrylate and bis-hydroxymethyl butyric acid in vacuum oven at 40 deg.C to remove water, and placing in CaCl₂The dryer of (3) is placed for 72 hours at 25 ℃;

2) HMDI in a molar amount of 60 parts was placed in the reactor and adjustedThe reaction temperature is 70-75 ℃, the stirring speed is 1500rpm, and N is introduced₂Protection, N₂A condensation recovery device with the temperature of 5 ℃ is arranged at an outlet, then a dimethyl carbonate solution in which 3 parts by mole of trimethylolpropane and 7 parts by mole of castor oil are dissolved is slowly dripped, and the reaction is continued for 1 hour after the dripping is finished;

3) adjusting the reaction temperature to 60 ℃, dropwise adding 18 parts of hydroxyethyl methacrylate into the reactor in the step 2), wherein the dropwise adding time is 1h, and the stirring speed is 3000 rpm;

4) further reducing the reaction temperature to 40 ℃, keeping the stirring speed unchanged, adding potassium persulfate into the product obtained in the step 3), slowly dropwise adding 54 parts of MMA monomer in a molar amount for 1h, and rapidly adding phenol after the dropwise adding is completed, wherein the addition amount of the phenol is 0.5% of the mass of the MMA;

5) adjusting the stirring speed to 3000rpm, adjusting the reaction temperature to 60 ℃, dropwise adding 8 parts by mole of bis (hydroxymethyl) butyric acid into the product obtained in the step 4), continuing to react for 1h after dropwise adding is finished, then adding 8 parts by mole of triethylamine at one time, stirring for 30min, and removing the redundant dimethyl carbonate solvent in the reactant by a vacuumizing and heating mode until no bubbles are generated in the viscous liquid;

6) deionized water is added to adjust the solid content to be 50 wt%, and the mixture is stirred uniformly after a defoaming agent is added, so that the component A of the environment-friendly color pavement surface layer protective agent is obtained.

The preparation method of the component B of the environment-friendly color pavement surface protective agent comprises the following steps:

1) placing 40 parts by molar weight of hexahydrophthalic acid diglycidyl ester into a reactor, adjusting the reaction temperature to 60 ℃, stirring at 1500rpm, introducing nitrogen for protection, and dropwise adding 15 parts by molar weight of polyetheramine D400 to obtain an epoxy resin prepolymer;

2) weighing 50 parts of castor oil by molar weight, adding boron trifluoride diethyl etherate, wherein the mass of the boron trifluoride diethyl etherate is 0.5 percent of that of the castor oil, uniformly stirring, adjusting the reaction temperature to 60 ℃, introducing nitrogen for protection, and adjusting the stirring speed to 1500 rpm;

3) slowly dripping the epoxy resin prepolymer prepared in the step 1) into the mixture in the step 2), wherein the dripping time is 2h, stirring and reacting for 6h at 60 ℃, the stirring speed is 1500rpm, and dripping DMC to adjust the viscosity of the product;

4) keeping the reaction temperature and the stirring speed unchanged, dropwise adding 20 parts of HMDI (dimethyl formamide) subjected to DMPA (dimethyl formamide) grafting modification into the product obtained in the step 3), and continuing to react for 1h after the dropwise addition is finished;

5) keeping the temperature and the rotating speed unchanged, adding 20 parts by mole of triethanolamine to neutralize the product obtained in the step 4), vacuumizing to remove redundant DMC until no bubbles are generated in the reactant liquid, slowly dropwise adding deionized water to prepare a dispersion liquid with the solid content of 50 wt%, and continuously stirring after dropwise adding until no foaming or wire drawing phenomenon occurs, thus obtaining the component B of the environment-friendly color pavement surface layer protective agent.

In the synthesis of the environment-friendly color antiskid pavement adhesive:

the feeding speed and the reaction temperature are strictly controlled, and particularly in the processes of polyurethane prepolymerization and polyurethane modified epoxy resin, the feeding speed and the reaction temperature are key factors influencing the success of experiments, and the gel or implosion reaction can be caused when the temperature and the stirring speed are not proper.

After the polyurethane modified epoxy resin is finished, the organic solvent dimethyl carbonate needs to be recycled in a vacuum pumping manner, and if the recycling is not clean, the problems of layering, incomplete emulsification, overlarge emulsion viscosity and the like in the subsequent emulsification process can be caused. In the preparation process of the B component of the environment-friendly color antiskid pavement adhesive, the tetrahydrophthalic acid diglycidyl ester is adopted to improve the compatibility of the B component and E51 in the A component, which is beneficial to the faster reaction of the two components in the curing process of the adhesive, and the tetrahydrophthalic acid diglycidyl ester has better space rotation capability compared with E51, and the existence of unsaturated bonds also improves the water loss resistance of the whole system after the curing reaction of the adhesive is finished and is better than linear glycidyl ester.

In the synthesis process of the environment-friendly color antiskid pavement surface layer protective agent:

the reaction temperature and the reaction speed need to be controlled, a polyurethane catalyst cannot be added in the polymerization process of polyurethane, the problem that the storage stability of a product is not enough due to catalyst residue and the problem that a spraying machine is difficult to construct due to the fact that the viscosity of a sample is increased in the later period is solved. In the experimental process, the HMDI type isocyanate is adopted, so that yellowing and pulverization caused by ultraviolet aging of isocyanate with a benzene ring structure can be prevented, and meanwhile, compared with the isocyanate with a benzene ring structure, the HMDI is low in reaction activity and has longer operation time, but compared with HDI, the HMDI is high in reaction activity, and the problem of overlong real drying time is avoided.

When the MMA is grafted and modified by the polyurethane prepolymer, the reaction temperature and the stirring speed need to be controlled, so that heat emitted by MMA free radical polymerization can be timely dissipated, the MMA addition speed is controlled, the prepolymer is prevented from being gelled due to implosion, and a small amount of phenol is added after the reaction is finished, so that the instability of a system caused by further self-polymerization of the incompletely reflected acrylic acid radicals in the heavy-end chain of the polyurethane prepolymer can be effectively prevented.

The prepolymerization process in the components A and B of the surface layer protective agent is mainly characterized in that the reaction activity of isocyanate and castor oil is low, the molecular weight is small, the film forming after construction is difficult to realize without prepolymerization, and the incomplete reaction of the surface layer protective agent is caused by low polymerization degree.

TMP and castor oil both have the function of graft modification, but castor oil is introduced mainly to improve the molecular weight of a prepolymer, too low TMP content is easy to cause the node density reduction of a crosslinking reaction to cause poor strength, and too high TMP content is easy to cause the soft end molecular weight of the prepolymer to be too short, and the toughness and ductility of the polymer are poor, so that the molar ratio of TMP to castor oil is selected to be 3:7 according to the comprehensive use requirement.

The invention has the advantages that:

1. the environment-friendly color anti-skid pavement adhesive prepared by the invention is subjected to polyurethane toughening modification, the waterborne epoxy resin subjected to polyurethane toughening modification has a good toughening effect, the elongation at break can reach 8.3%, the tensile strength can still keep a high value (31.7MPa), and the shear strength is remarkably improved compared with that of the waterborne epoxy resin sold in the market and can reach 17.27 MPa; the tensile strength, the elongation at break and the shear strength have better matching performance, so that the crack resistance and the fatigue resistance of the prepared colorful antiskid pavement are obviously improved;

2. the PEG structure with high molecular weight is introduced in the process of the prepared polyurethane graft modified epoxy resin, so that the epoxy resin has certain emulsifying capacity, and E51 can be emulsified into stable emulsion, but the emulsifying capacity is poorer than that of an emulsifier in the existing water-based epoxy resin, mainly because the molecular weight occupied by hydrophilic groups in the polyurethane modified epoxy resin is relatively lower, and because the water loss resistance of a final product is obviously weakened due to the introduction of more hydrophilic groups, more hydrophilic molecular connecting segments are introduced as little as possible under the condition of ensuring certain emulsifying capacity by comprehensive consideration and selection;

3. HMDI and refined castor oil are introduced into the polyurethane modified epoxy resin, and hydrogenated bisphenol A epoxy resin adopted by the epoxy resin has better space activity and rotation capability, so that the elongation at break and shear strength resistance of the environment-friendly color pavement adhesive are better;

4. the use of the surface layer protective agent effectively improves the anti-stripping capability of the ceramic particles of the colored anti-skid pavement and further improves the water loss resistance of the environment-friendly colored anti-skid pavement.

Detailed Description

In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.

Example 1:

firstly, preparing an environment-friendly color anti-skid pavement adhesive A component:

1) drying oleum ricini (purity 99.5%), polyethylene glycol 2000, dimethyl carbonate, and 4,4' -dicyclohexylmethane diisocyanate (HMDI) in a vacuum drying oven at 40 deg.C to remove water, and placing in CaCl₂The dryer (2) is placed for 72 hours at the temperature of 25 ℃;

2) a mixture of castor oil in a molar amount of 10 parts and polyethylene glycol in a molar amount of 10 parts (molecular weight 2000) is dissolved in dimethyl carbonate in a molar amount of 30 parts and, at a temperature of 45 c,placing in a reactor, stirring until completely dissolved, and then supplying 99.99% of N to the reactor₂Protection, the reactor is heated by adopting oil bath, the reaction temperature is adjusted to 70 ℃, the mechanical stirring speed is 3000rpm, N₂A condensation recovery device with the temperature of 5 ℃ is arranged at an outlet and is used for collecting the evaporated dimethyl carbonate, the reaction temperature needs to be controlled in the reaction process, the stirring speed is accelerated, and the phenomena of implosion reaction and gel agglomeration caused by the fact that the heat release in the reaction process cannot be timely dissipated are prevented;

3) weighing 20 parts by molar weight of 4,4' -dicyclohexylmethane diisocyanate (HMDI for short), slowly dripping into the reactor of 2), wherein the dripping speed is 10mol/h, keeping the reaction condition unchanged after the dripping is finished, and continuously reacting for 3h to obtain a reaction product I;

4) weighing 15 parts of diglycidyl hexahydrophthalate, placing the diglycidyl hexahydrophthalate in a reactor, providing nitrogen protection, adjusting the reaction temperature to 70 ℃, stirring at 1500rpm, adding boron trifluoride diethyl etherate with the mass fraction of 0.5% of the diglycidyl hexahydrophthalate, uniformly stirring, slowly dropwise adding a reaction product (I) for 3 hours, and continuously stirring for reacting for 2 hours after dropwise adding to obtain a reaction product (II); in the reaction process, the stirring speed needs to be controlled to ensure that the reaction is more complete, the reaction temperature is reduced, and the phenomenon that the reaction degree of NH & lt- & gt and epoxy groups in polyurethane is deepened due to overhigh temperature to cause the gel curing of the polyurethane modified epoxy resin is prevented;

5) heating the reaction product to 80 ℃ and stopping introducing N₂In N at₂A 5 ℃ condensation recovery device at an outlet is connected with a vacuum pump for vacuum pumping operation, the stirring speed of the reactor is adjusted to 3000rpm, constant-temperature and constant-speed vacuum pumping treatment is carried out for 1h, a large amount of bubbles are generated in a reaction product II at the beginning, and a light yellow transparent mucus substance is obtained as a reaction product III until no bubbles are generated;

6) adding 85 parts of bisphenol A epoxy resin E51 into the reaction product (c), adjusting the reaction temperature to 60 ℃, adjusting the stirring speed to 3000rpm, removing the vacuumizing device, communicating the whole reaction equipment with the atmosphere, slowly adding deionized water dropwise, keeping the temperature and the stirring speed unchanged after dropwise addition for 30min, and continuously stirring for 30min to prepare a modified epoxy resin emulsion with 50% of solid content;

7) adding stabilizer PVA with the mass of 0.5 percent of the total mass of the fourth agent and 0.5 percent of flatting agent alkyl modified organosiloxane into the mixture of 6), and continuing stirring for 15min until homogeneous milky emulsion is formed, namely the component A of the environment-friendly color anti-skid pavement adhesive.

Secondly, preparing an environment-friendly color anti-skid pavement adhesive B component:

1) weighing 70 parts by mole of methylcyclopentanediamine (TAC-900) and 10 parts by mole of polyetheramine D400, heating to 60 ℃, stirring and mixing uniformly, and introducing nitrogen for protection;

2) slowly dripping 80 parts by molar weight of tetrahydrophthalic acid diglycidyl ester into the mixture obtained in the step 1), keeping the dripping speed at 60 ℃ and stirring for 12 hours at 1500rpm until the liquid becomes brown yellow viscous liquid;

3) slowly dripping 20 parts of hexanediol diglycidyl ether into the reactor 2), wherein the dripping speed is 0.5 part/min, stirring is carried out for 8 hours at 60 ℃, the stirring speed is 1500rpm, the viscosity of the liquid is gradually increased, the color is still brown yellow viscous liquid, the dripping speed and the reaction temperature cannot be too high, and the phenomenon of gel can be caused if the dripping speed and the reaction temperature are too high;

4) keeping the temperature and the rotating speed unchanged, slowly dripping deionized water into the mixture in step 3) to prepare brown yellow homogeneous liquid with the solid content of 50%, and continuously stirring the mixture after dripping until no foaming and no wire drawing phenomenon occur, thus obtaining the component B of the environment-friendly color anti-slip pavement adhesive.

Thirdly, preparing an environment-friendly colorful antiskid pavement surface layer protective agent A component:

1) drying oleum ricini (purity 99.5%), Trimethylolpropane (TMP), dimethyl carbonate (DMC), HMDI, hydroxyethyl methacrylate and bis-hydroxymethyl butyric acid (DMBA) in vacuum oven at 40 deg.C to remove water, and placing in CaCl₂The dryer (2) is placed for 72 hours at the temperature of 25 ℃;

2) HMDI in a molar amount of 60 parts was placed in the reactor and adjustedThe whole reaction temperature is 70-75 ℃, the stirring speed is 1500rpm, and N is introduced₂Protection, N₂A condensation recovery device with the temperature of 5 ℃ is arranged at an outlet and is used for collecting the evaporated dimethyl carbonate (the molecular weight of the prepolymer is increased too fast due to overhigh reaction temperature, so that the subsequent grafting modification is difficult, and the catalyst is not added so as to control the reaction speed), then the DMC solution dissolved with TMP and castor oil (the molar weight of the TMP is 3 parts and the molar weight of the castor oil is 7 parts) is slowly dripped at the dripping speed of 5 mol parts/h, and the reaction is continued for 1h after the dripping is finished;

3) adjusting the reaction temperature to 60 ℃, dropwise adding 18 parts by mole of hydroxyethyl methacrylate (HEMA) into the mixture in the step 2), wherein the dropwise adding time is 1h, and the stirring speed is 3000rpm (reducing the reaction speed, improving the heat release and preventing HEMA self-polymerization);

4) further reducing the reaction temperature to 40 ℃, keeping the stirring speed unchanged, adding potassium persulfate into the mixture 3), wherein the mass of the potassium persulfate is 0.5 percent of that of HEMA, slowly dropwise adding 54 parts of MMA monomer in a molar amount for 1h, and rapidly adding phenol after the dropwise adding is completed, wherein the addition amount of the phenol is 0.5 percent of that of the MMA (preventing the MMA graft modified polyurethane prepolymer from generating gel agglomeration caused by free radical polymerization);

5) stirring speed is adjusted to 3000rpm, reaction temperature is adjusted to 60 ℃, 8 parts of DMBA with molar weight is dripped into the mixture 4), dripping speed is 2 parts/h, reaction is continued for 1h after dripping is finished, then triethylamine with molar weight of 8 parts is added at one time for stirring for 30min, and then redundant DMC solvent in reactants is removed in a vacuumizing and heating mode until no bubbles are generated in viscous liquid;

6) then deionized water is added to adjust the solid content to be 50 percent, and polyether modified organic silicon type defoaming agent with the total solid content of 0.5 percent by weight is added and stirred evenly, thus preparing the component A of the environment-friendly colorful antiskid pavement surface layer protective agent.

Fourthly, preparing an environment-friendly color antiskid pavement surface layer protective agent B component:

1) placing 40 parts by molar weight of hexahydrophthalic acid diglycidyl ester into a reactor, adjusting the reaction temperature to 60 ℃, stirring at 1500rpm, introducing nitrogen for protection, and dropwise adding 15 parts by molar weight of polyetheramine D400 at 5 parts/h to obtain an epoxy resin prepolymer;

2) weighing 50 parts of castor oil by molar weight, adding boron trifluoride diethyl etherate accounting for 0.5% of the mass of the castor oil, uniformly stirring, adjusting the reaction temperature to 60 ℃, introducing nitrogen for protection, and adjusting the stirring speed to 1500 rpm;

3) slowly dripping the epoxy resin prepolymer prepared in the step 1) into the step 2), wherein the dripping time is 2h, the temperature is kept at 60 ℃, stirring reaction is carried out for 6h, the stirring speed is 1500rpm, and DMC is added after the reaction is finished to adjust the viscosity of the product;

4) keeping the reaction temperature and the stirring speed unchanged, dropwise adding 20 parts of HMDI (dimethyl formamide) subjected to DMPA (dimethyl formamide) grafting modification into the mixture in the step 3), wherein the dropwise adding speed is 5 parts/h, and continuously reacting for 1h after the dropwise adding is finished;

5) keeping the temperature and the rotating speed unchanged, adding 20 parts by mol of triethanolamine to neutralize the product of 4) at one time, then vacuumizing to remove redundant DMC until no bubbles are generated in reactant liquid, then slowly dripping deionized water to prepare a dispersion liquid with the solid content of 50%, and continuously stirring after dripping until no foaming or wire drawing phenomenon occurs, thus obtaining the component B of the environment-friendly color antiskid pavement surface layer protective agent.

Fifthly, preparing the anti-stripping environment-friendly color anti-skid pavement:

1) cleaning and sweeping the constructed pavement, wherein the constructed ground needs to be clean, free of oil stain, pulverization, clear water and floating ash;

2) repairing the damaged part of the base surface by using epoxy mortar, wherein the surface of the concrete needs to be clean, dry and firm;

3) mixing 100 parts by mass of an environment-friendly color anti-skid pavement adhesive A component, 150 parts by mass of an environment-friendly color anti-skid pavement adhesive B component, 100 parts by mass of tap water and 10 parts by mass of pigment; stirring uniformly by a stirrer at the stirring speed of 1500rpm for 5min until the emulsion presents uniform pigment color;

4) pouring the prepared environment-friendly color anti-skid pavement adhesive on a construction pavement, spreading the environment-friendly color anti-skid pavement adhesive by using a serrated rubber scraper (the width of each sawtooth is 2mm, and the depth of each sawtooth is 3mm), and waiting for the environment-friendly color anti-skid pavement adhesive to automatically flow to be completely flat;

5) spreading color ceramic particles with the particle size of 1-3mm from top to bottom until the color ceramic particles completely cover the environment-friendly color anti-skid pavement adhesive;

6) after the environment-friendly color anti-skid pavement adhesive is completely solidified (more than or equal to 24 hours), sweeping the color ceramic particles which are not completely bonded on the surface by using a broom, and uniformly sweeping by using a pavement sweeping tool;

7) after the surplus aggregate is collected, mixing the components A and B of the environment-friendly colorful anti-skid pavement surface protective agent according to the mass ratio of 1.5:2, adding water to adjust the viscosity of the whole surface protective agent, and spraying the surface protective agent on the pavement surface by a spraying machine, wherein the spraying amount is 0.5kg/m²(ii) a After the pavement is dried, the anti-stripping environment-friendly color antiskid pavement can be prepared.

The performance evaluation of the prepared environment-friendly color anti-skid pavement adhesive comprises the following steps:

1) a part of the prepared environment-friendly color antiskid pavement adhesive is reserved for mechanical property testing, and the rest is prepared into a wet wheel abrasion test piece.

2) In order to better test the service life of the color antiskid pavement prepared from different materials, the invention adopts an accelerated loading fatigue tester to test, a prototype AC-13 asphalt mixture test piece is manufactured, the thickness of the prototype AC-13 asphalt mixture test piece is 5cm, then the color antiskid pavement is paved on the surface layer of the test piece according to the color antiskid pavement construction method, and redundant ceramic particles on the surface are cleaned after the color antiskid pavement is cured at room temperature. Weighing mass m of test block on unpaved color antiskid road surface₀Paving color antiskid pavement and collecting the mass m of the test block after the excessive aggregate is collected₁After the accelerated loading fatigue test is finished, cleaning the redundant ceramic particles and waste materials suspended on the surface, and weighing the mass m of the test piece again₂And the fatigue resistance of the colored antiskid pavement is measured by the mass loss proportion.

Fatigue resistance p ═ m₁-m₂)/(m₁-m₀)*100％

3) And (3) testing environmental protection performance: the environmental protection performance of the material is evaluated by testing the content of VOCs in the adhesive;

4) and (3) testing the storage stability of the emulsion: observing test layering conditions after centrifuging at 3000rpm for 30 min;

5) and (3) viscosity testing: investigating the flow property of the mixed adhesive for investigating the actual construction performance;

6) curing time: the method is used for inspecting the construction closing time and measuring the open traffic time in the actual construction process;

7) and (3) testing mechanical properties: the method is used for evaluating the mechanical property and the shrinkage rate of the material.

Comparative example 1:

conventional waterborne epoxy adhesives: the wear-resistant paint is prepared from a water-based epoxy resin emulsion (Wuhanshi Quanxing new material science and technology Co., Ltd.) and a water-based epoxy resin curing agent (Shandong Haoyao new material Co., Ltd.) in a mass ratio of 1:1, 5 wt% of pigment is added, a part of the paint is left after uniform stirring for mechanical property testing, and the rest part of the paint is prepared into a wet wheel wear test piece. The performance test method was the same as in example 1.

Comparative example 2:

polyurethane adhesive: prepared from 3070 resin (Henan Si Deg chemical engineering Co., Ltd.) and MDI-50 curing agent (Wanhua chemical group Co., Ltd.) in a ratio of 4:1, 5 wt% of pigment is added, a part is left after stirring uniformly for mechanical property test, and the rest is prepared into a wet wheel abrasion test piece. The performance test method was the same as in example 1.

Comparative example 3:

MMA adhesive: the test piece is prepared from MMA resin (Taiyuan Chengni science and technology Co., Ltd.) and dibenzoyl peroxide initiator in a mass ratio of 100:2, 5 wt% of pigment is added, a part of the mixture is left after stirring uniformly for mechanical property test, and the rest is prepared into a wet wheel abrasion test piece. The performance test method was the same as in example 1.

The results of the above performance tests are shown in the following table, with the test methods referenced to the relevant standards.

The results of experiments show that the performance of the environment-friendly colorful anti-skid pavement material prepared by the invention is superior to that of the conventional waterborne epoxy resin and polyurethane on the whole, the fatigue resistance is inferior to that of MMA, but the environmental performance is superior to that of MMA.

The environment-friendly color anti-skid pavement added with the surface layer protective agent has the advantages that the water loss resistance and fatigue test performance are remarkably improved, and a sandwich structure is formed mainly by the environment-friendly color adhesive, the ceramic particles and the surface layer protective agent, so that the ceramic particles have better embeddability and better abrasion resistance.