Tunnel brightening modified epoxy mortar and preparation method thereof

Abstract

The invention provides tunnel brightening modified epoxy mortar and a preparation method thereof. The raw materials of the epoxy mortar at least comprise a component A and a component B, the component A comprises epoxy resin, aggregate and a reflective material; the component B comprises a curing agent and an auxiliary agent; wherein the aggregate comprises modified polyether-ether-ketone particles; pEEK powder is modified and added, so that the environment resistance is enhanced, and the surface pollution risk is reduced; the hydrophobicity of the epoxy mortar is enhanced, the accumulation of static electricity generated by friction of vehicle tires can be reduced, and the driving safety is improved; mechanical properties of the mortar are improved, the mortar adapts to a high-temperature environment of vehicle tail gas in a tunnel, and tolerance is improved; the epoxy resin, the modified PEEK and the reflective material form an energy transition layer, and the gradient design effectively reduces the interfacial tension difference between the glass beads and the epoxy matrix, inhibits the agglomeration of the beads, and enhances the structural stability; the reflective characteristic of the same system is further enhanced.

Description

TECHNICAL FIELD

[0001] The present application relates to an epoxy mortar coating, in particular to a tunnel brightening modified epoxy mortar and a preparation method thereof. BACKGROUND

[0002] As a core underground transportation facility, the internal environment of the tunnel is subjected to the coupling effect of multiple factors such as humidity, vibration, tail gas corrosion, etc., which leads to cracks, leakage and surface deterioration of the concrete lining. The traditional epoxy mortar, with high bonding strength (> 3 MPa) and rapid curing characteristics, has become the mainstream material for tunnel repair. However, with the promotion of smart tunnel and low-carbon operation and maintenance concept, single mechanical repair cannot meet the demand. According to the survey, the energy consumption of tunnel lighting accounts for more than 35% of the total operation cost, and the low reflectivity (60° gloss < 10GU) of the traditional epoxy mortar aggravates the lighting load. Therefore, the development of brightening epoxy mortar with structural repair and optical enhancement functions has become a research hotspot in recent years.

[0003] Existing research mainly improves the optical performance of epoxy mortar by adding reflective fillers such as glass beads and titanium dioxide. For example, Zhang et al. used 20% glass beads to dope the system, which increased the reflectivity of the material to 65%, but the compressive strength decreased from 80 MPa to 62 MPa. Chen's team proposed a nano-TiO pre-mixing process with epoxy resin, which achieved 85% visible light reflectivity under ultraviolet light, but the agglomeration of nanoparticles led to an 18% decrease in interfacial bonding strength. In addition, some scholars tried to introduce rare earth complexes to achieve active light emission, but their weather resistance has not yet reached the engineering standard.

[0004] The current brightening epoxy mortar faces three major contradictions: 1. Optical-mechanical performance antagonism: the rigid characteristics of reflective fillers are incompatible with the flexible network of the epoxy matrix, causing stress concentration; 2. Longevity and environmental adaptability imbalance: acidic tail gas leads to the loss of photocatalytic activity of titanium dioxide, and the reflectivity decreases by 40%; 3. Conflict of construction rheological properties: it is difficult to balance the requirements of low viscosity and anti-sagging, and the efficiency of spray coating is reduced by 50%.

[0005] In summary, the current tunnel brightening epoxy mortar faces technical bottlenecks such as reflective characteristics and mechanical properties, short service life, and poor reflective effect. This puts higher requirements on the research and development of new coating materials, which needs to consider the selection of particulate materials, modification of matrix resin, and optimization of coating process to achieve the coordination and unity of durability, reflectivity, and mechanical properties. SUMMARY

[0006] The technical problem to be solved by the present application is to overcome the deficiencies in the prior art and provide a tunnel brightening modified epoxy mortar and a preparation method thereof.

[0007] In a first aspect, the present application provides a tunnel lightening modified epoxy mortar, raw materials of the epoxy mortar at least including A component and B component; the A component includes epoxy resin, aggregate and reflective material; the B component includes curing agent and auxiliary agent;

[0008] The aggregate includes modified polyether ether ketone microparticles; the modified polyether ether ketone is prepared by taking 4,4-difluorobenzophenone, 3,3-(2,4-diamino-6,7-pteridine diyl)diphenol and 2,2,3,4,4,5,5-octafluoro-1-pentanol as raw materials, taking N,N-dimethylacetamide (DMAc) as solvent, taking hydroquinone as terminator and taking alkali catalyst for catalysis.

[0009] The modification of polyether ether ketone can change the regularity of polymer molecular chain, increase the amorphous aggregate structure of polymer molecular chain, make the polymer have good dispersion performance, increase the polarity of polymer molecular chain and reduce the interaction force between molecules, further improve the dispersion effect of aggregate in the epoxy mortar system, make the epoxy mortar have shear thinning characteristics and enhance the workability of the mortar.

[0010] In some embodiments, the preparation method of the modified polyether ether ketone includes the following steps:

[0011] (1) N,N-dimethylacetamide, 4,4-difluorobenzophenone and alkali catalyst are added into a reactor, inert gas is introduced and stirred uniformly;

[0012] (2) 3,3-(2,4-diamino-6,7-pteridine diyl)diphenol is added into the reaction system, heated and reacted, and hydroquinone is added to terminate the reaction;

[0013] (3) 2,2,3,4,4,5,5-octafluoro-1-pentanol is added into the above reaction system, heated at 30-80℃ for 2-8h, and after the reaction is completed, the solvent is evaporated, precipitated, filtered and dried to obtain the modified polyether ether ketone.

[0014] In some embodiments, the addition molar ratio of 4,4-difluorobenzophenone, 3,3-(2,4-diamino-6,7-pteridine diyl)diphenol and 2,2,3,4,4,5,5-octafluoro-1-pentanol is 1-1.2:1:0.5-1.

[0015] In some embodiments, the alkali catalyst is selected from one or more combinations of sodium hydroxide, potassium hydroxide, potassium carbonate or sodium carbonate; and the addition molar amount of the alkali catalyst is 0.1-0.5 times of the addition molar amount of 3,3-(2,4-diamino-6,7-pteridine diyl)diphenol.

[0016] In some embodiments, the particle size of the aggregate is 20-50 μm; too fine particle size can easily cause the viscosity of the epoxy system to surge, and too coarse particle size can weaken the interfacial bonding force; controlling the size of the aggregate can help reduce the viscosity of the mixed system and facilitate construction pumping.

[0017] In some embodiments, the epoxy resin is selected from one or more combinations of E51 type epoxy resin, E44 type epoxy resin, E12 type epoxy resin, and E100 type epoxy resin; the epoxy resin with a suitable molecular weight or structure can be selected according to the actual application.

[0018] In some embodiments, the aggregate can further include one or more combinations of the group consisting of aluminum oxide, talc powder, mica powder, red calcium powder, quartz sand, and aluminum silicate ceramic powder.

[0019] For example, the quartz sand can be black, blue, red, white, etc., to provide a certain aesthetic appearance for the epoxy mortar.

[0020] In some embodiments, the reflective material is glass beads with a specification of 100-500 mesh.

[0021] In some embodiments, the curing agent is selected from one or more combinations of amine curing agents, acid anhydride curing agents, and polyamine curing agents; preferably, the curing agent is an amine curing agent, such as one or more combinations of triethylenetetramine, diethylenetriamine, isophorone diamine, 4,4'-diaminodiphenyl methane, and diaminodiphenyl sulfone.

[0022] In some embodiments, the auxiliary agent can be selectively added according to actual needs, such as one or more combinations of a toughening agent, a plasticizing agent, a thickening agent, an anti-ultraviolet agent, an antistatic agent, a moisture-proof agent, or a preservative; the present application does not make special limitations on the types of auxiliary agents.

[0023] In some embodiments, the raw materials of the epoxy mortar coating include at least A component and B component; the A component includes modified epoxy resin 30-50 parts, aggregate 1-15 parts, and reflective material 10-30 parts; the B component includes curing agent 5-15 parts and auxiliary agent 0.1-10 parts.

[0024] Further, the raw materials of the epoxy mortar coating include at least A component and B component; the A component includes modified epoxy resin 30-50 parts, aggregate 3-5 parts, and reflective material 10-30 parts; the B component includes curing agent 5-15 parts and auxiliary agent 0.1-10 parts.

[0025] In a second aspect, the present application provides a preparation method of the above-mentioned weather-resistant and wear-resistant epoxy mortar coating for signs, specifically including the following steps:

[0026] Preparation of A component: add epoxy resin into the container under low speed stirring at 300-700 rpm, and disperse at low speed for 5-10 min at 300-700 rpm; then add aggregate and disperse at high speed at 1000-1500 rpm; then add reflective material and disperse at low speed for 10-15 min at 300-700 rpm, to obtain A component;

[0027] Preparation of B component: add curing agent and auxiliary agent into the container under low speed stirring at 50-100 rpm, and disperse at 500-700 rpm for 5-10 min, to obtain B component.

[0028] Beneficial effects

[0029] 1. By adding PEEK powder for modification, the environmental resistance is enhanced, and the risk of surface pollution is reduced; the hydrophobicity of the epoxy mortar is enhanced, the static electricity accumulation generated by the friction of vehicle tires can be reduced, and the driving safety is improved; the mechanical properties of the mortar are improved, the high-temperature environment of vehicle exhaust in the tunnel is adapted, and the tolerance is improved.

[0030] 2. The energy transition layer is formed by the epoxy resin, the modified PEEK and the reflective material, the gradient design effectively reduces the interfacial tension difference between the glass microbeads and the epoxy matrix, inhibits the aggregation of the microbeads, and enhances the structural stability; the reflective characteristics of the same system are further enhanced. DETAILED DESCRIPTION

[0031] The following embodiments of the application are further described, and it should be pointed out that the specific embodiments described herein are only for the purpose of illustrating and explaining the application, and are not limited to the application.

[0032] The mica powder used in the embodiments of the application has a specification of 20 mesh; the glass microbeads used are purchased from Gongyi Chenyi Refractory Abrasive Co., Ltd., and the item number is kxwz00019.

[0033] Preparation of modified polyether ether ketone powder 1

[0034] (1) 100ml N,N-dimethylacetamide, 5mol 4,4-difluorobenzophenone, 0.5mol KOH were added into the reactor, nitrogen was introduced, and stirring was uniform;

[0035] (2) 5mol 3,3-(2,4-diamino-6,7-pteridine diyl) diphenol was added into the reaction system, heated at 280℃ for 6h, and 1mol p-phenylenediamine was added to terminate the reaction;

[0036] (3) Add 2.5 mol of 2,2,3,4,4,5,5-octafluoro-1-pentanol to the above reaction system, heat at 50°C for 6 h, and after the reaction is completed, evaporate the solvent, precipitate, filter and dry to obtain modified polyether ether ketone.

[0037] The modified polyether ether ketone masterbatch was frozen at -30°C for 4 hours, and then finely crushed to 20μm using a step-by-step crushing process of jaw crusher, hammer mill, and air jet mill.

[0038] The synthesized modified polyetheretherketone powder was analyzed by Fourier transform infrared spectroscopy using potassium bromide pellets. The infrared spectrum of the reaction product showed that:

[0039] At 1355cm -1 It exhibits a strong absorption characteristic peak of -CF at 1600 cm⁻¹; -1 Vibrations of conjugated systems of heterocyclic C=N and C=C containing pteridine; 1550 cm -1 There is vibration of the aromatic ring C=C skeleton, 1650 cm. -1 The presence of C=O stretching vibrations indicates that the above steps successfully prepared the modified polyether ether ketone powder.

[0040] Preparation of modified polyetheretherketone powder 2

[0041] The modified polyether ether ketone powder 2 was prepared by adding 4 mol of 2,2,3,4,4,5,5-octafluoro-1-pentanol, which is basically the same as modified polyether ether ketone powder 1.

[0042] Preparation of modified polyetheretherketone powder 3

[0043] The modified polyether ether ketone powder 3 was prepared by adding 5 mol of 2,2,3,4,4,5,5-octafluoro-1-pentanol, which is basically the same as modified polyether ether ketone powder 1.

[0044] Preparation of modified polyetheretherketone powder 4

[0045] The modified polyether ether ketone powder 1 is basically the same as that of modified polyether ether ketone powder 1, except that the modified polyether ether ketone is finely crushed to 50 μm to prepare modified polyether ether ketone powder 4.

[0046] Preparation of modified polyetheretherketone powder 5

[0047] The modified polyether ether ketone powder 5 was prepared by adding 0 mol of 2,2,3,4,4,5,5-octafluoro-1-pentanol, which is basically the same as modified polyether ether ketone powder 1.

[0048] Preparation of modified polyetheretherketone powder 6

[0049] The modified polyether ether ketone powder 6 was prepared basically the same as the modified polyether ether ketone powder 1, except that the modified polyether ether ketone was finely ground to 10 μm.

[0050] The modified polyether ether ketone powder 7 was prepared basically the same as the modified polyether ether ketone powder 1, except that the modified polyether ether ketone was finely ground to 60 μm.

[0051] The modified polyether ether ketone powder 7 was prepared basically the same as the modified polyether ether ketone powder 1, except that the modified polyether ether ketone was finely ground to 60 μm.

[0052] The polyether ether ketone powder 8 was purchased from Dongguan Zhangmutou Jinyunlai Plastic Raw Material Operating Department, polyether ether ketone fine powder, 20 μm.

[0053] The polyether ether ketone powder 8 was purchased from Dongguan Zhangmutou Jinyunlai Plastic Raw Material Operating Department, polyether ether ketone fine powder, 20 μm.

[0054] Example

[0055] The raw materials were weighed according to the following table.

[0056] Preparation of A component: the epoxy resin was added to the container under low speed stirring at 300 rpm, and dispersed at 700 rpm for 10 min; the aggregate was added and dispersed at 1000 rpm for 10 min; the reflective material was added and dispersed at 500 rpm for 10 min, to obtain the A component;

[0057] Preparation of B component: the curing agent and the additive were added to the container under low speed stirring at 100 rpm, and dispersed at 500 rpm for 10 min, to obtain the B component.

[0058] Table 1: Raw materials and added parts (weight parts) of each example

[0059]

[0060]

[0061] Table 2: Raw materials and added parts (weight parts) of each comparative example

[0062]

[0063] The epoxy mortar of each example and comparative example after paving was tested according to the following methods:

[0064] 1. Compressive strength: tested according to GB / T 17671-1999, the higher the value, the better the compressive strength.

[0065] 2. Wear resistance: tested according to GB / T 22374-2008, the wear loss less than 0.030 g is qualified.

[0066] 3. Adhesion: tested according to standard GB / T9286-1998, the test results are graded according to an integer in 0-5, the value increases the worse adhesion, wherein 0 level indicates intact, 4 level indicates that the layer along the cutting edge large pieces of peeling, and / or some grid partial or total peeling, affected by the cross-cut area is significantly greater than 35%, but can not be significantly greater than 65%, 5 level indicates that the degree of peeling exceeds 4 level.

[0067] 4. Diffuse reflection coefficient: diffuse reflection light scattered by the sample surface is collected by an integrating sphere device, and the diffuse reflection coefficient is calculated by comparing the reflectivity of a standard white plate (BaSO). The wavelength range of the integrating sphere spectrometer is 380-2500 nm, and the resolution is ≤5 nm; the diffuse reflection coefficient is ≥85% for good.

[0068] 5. Extension diameter: the 30 min flowability extension diameter is determined according to JC / T 1004-2017 "Ceramic tile jointing agent", and ≥120 mm is pass, and ≥200 mm is excellent.

[0069] Table 3 test results

[0070]

[0071] As can be seen from the experimental data in the table, the epoxy mortar material prepared in the examples has the characteristics of high compressive strength, high wear resistance, strong adhesion and good diffuse reflection performance, and the flowability extension diameter meets the requirements. At the same time, as can be seen from example 5, the modified polyether ether ketone in the application can be co-processed with epoxy resin, and excellent flowability of epoxy mortar is obtained. Without adding leveling agent, the flowability extension diameter is equal to or better than that of the group adding leveling agent.

[0072] Comparative example 1 does not use polyfluoride modified polyether ether ketone, resulting in reduced wear resistance and diffuse reflection coefficient, and is not easy to process.

[0073] Comparative examples 2-3 do not control the particle size of the modified polyether ether ketone within the required range, and the viscosity of the epoxy mortar system increases due to the fine powder, and the adhesion of the epoxy mortar decreases due to the coarse powder; comparative example 4 does not use the modified polyether ether ketone provided by the application, and the performance is not as good as the epoxy mortar provided by the example.

[0074] As can be seen from comparative example 5, it is because the epoxy resin, modified PEEK and reflective material form an energy transition layer that effectively reduces the interfacial tension difference between the glass beads and the epoxy matrix, inhibits the aggregation of the microbeads, and enhances the structural stability; it can further enhance the reflective properties in the same system.

[0075] The above embodiments are only for illustrating the technical concept and characteristics of the present application, and the purpose is to enable those skilled in the art to understand the present application and implement it, and cannot limit the protection scope of the present application, and any equivalent changes or modifications made according to the spirit and principle of the present application shall be covered within the protection scope of the present application.

Claims

1. A modified epoxy mortar for tunnel lighting, characterized in that, The epoxy mortar raw materials include at least component A and component B; component A includes epoxy resin, aggregate, and reflective material; component B includes curing agent and additives; The aggregate includes modified polyetheretherketone microparticles; the modified polyetheretherketone is prepared by using 4,4-difluorobenzophenone, 3,3-(2,4-diamino-6,7-pteridinediyl)diphenol, and 2,2,3,4,4,5,5-octafluoro-1-pentanol as raw materials, N,N-dimethylacetamide as solvent, hydroquinone as terminating agent, and an alkaline catalyst.

2. The modified epoxy mortar for tunnel lighting according to claim 1, characterized in that, The preparation method of the modified polyether ether ketone includes the following steps: (1) Add N,N-dimethylacetamide, 4,4-difluorobenzophenone and alkaline catalyst to the reactor, introduce inert gas and stir evenly; (2) Add 3,3-(2,4-diamino-6,7-pteridinediyl)diphenol to the reaction system, heat to increase the temperature to carry out the reaction, and add hydroquinone to terminate the reaction; (3) Add 2,2,3,4,4,5,5-octafluoro-1-pentanol to the above reaction system, heat to 30-80℃ and react for 2-8 hours. After the reaction is completed, evaporate the solvent, precipitate, filter and dry to obtain modified polyether ether ketone.

3. The modified epoxy mortar for tunnel lighting according to claim 2, characterized in that, The molar ratio of 4,4-difluorobenzophenone, 3,3-(2,4-diamino-6,7-pteridinediyl)diphenol and 2,2,3,4,4,5,5-octafluoro-1-pentanol is 1-1.2:1:0.5-1.

4. The modified epoxy mortar for tunnel lighting according to claim 1, characterized in that, The aggregate has a particle size of 20-50 μm.

5. The modified epoxy mortar for tunnel lighting according to claim 1, characterized in that, The epoxy resin is selected from one or more combinations of E51 type epoxy resin, E44 type epoxy resin, E12 type epoxy resin, and E100 type epoxy resin.

6. The modified epoxy mortar for tunnel lighting according to claim 1, characterized in that, The aggregate may also include one or more combinations of alumina, talc, mica, heavy calcium carbonate, quartz sand, and aluminosilicate ceramic powder.

7. The modified epoxy mortar for tunnel lighting according to claim 1, characterized in that, The curing agent is selected from one or more combinations of amine curing agents, acid anhydride curing agents, and polyamine curing agents.

8. The modified epoxy mortar for tunnel lighting according to claim 1, characterized in that, The epoxy mortar coating, by weight, comprises at least component A and component B; component A comprises 30-50 parts of modified epoxy resin, 1-15 parts of aggregate, and 10-30 parts of reflective material; component B comprises 5-15 parts of curing agent and 0.1-10 parts of additives.

9. The preparation method of the modified epoxy mortar for tunnel lighting according to any one of claims 1-8 comprises the following steps: Preparation of Component A: Add epoxy resin to the container under low-speed stirring at 300-700 rpm and disperse at low speed for 5-10 min at 300-700 rpm; then add aggregate and disperse at high speed at 1000-1500 rpm; then add reflective material and disperse at low speed at 300-700 rpm for 10-15 min to obtain Component A; Preparation of component B: Add curing agent and additives to the container under low-speed stirring at 50-100 rpm, and disperse at 500-700 rpm for 5-10 min to obtain component B.

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