A long-life road marking paint and its preparation method and application

Abstract

The present invention discloses a long-life road marking paint and a preparation method and application thereof, belonging to the technical field of road marking paint. The paint comprises the following raw materials by weight: 18-20 parts of organosilicon hybrid polylactic acid modified C5 petroleum resin, 5-6 parts of pigment, 52-53 parts of filler, 22-25 parts of glass microspheres, and 2.5-3 parts of additives. The preparation method comprises the following steps: weighing the raw materials according to weight, mixing them evenly, continuously heating to a molten state at 180-220°C, stirring evenly, cooling and crushing to obtain the paint. Application and preparation Road marking has better weather resistance. The present invention prepares a road marking paint with good wear resistance and aging resistance, which can greatly avoid cracking of the marking and improve the service life of the road marking paint.

Description

Technical Field

[0001] The invention belongs to the technical field of road marking paints, and in particular relates to a long-life road marking paint and a preparation method and application thereof. Background Art

[0002] Road marking paint refers to a special paint used to draw traffic markings on roads. According to different classification standards, road marking paint can be divided into many types, including hot melt type, room temperature solvent type, water-based paint and two-component paint.

[0003] Hot-melt road marking paint is currently the most widely used type of paint. It has the advantages of fast drying, good durability, and good night-time reflective effect. It is suitable for urban roads, highways, parking lots, etc. Normal temperature solvent-based road marking paint is a traditional road marking paint. Although it dries slowly and has a short service life, it has a low cost and is still widely used on some urban roads and general roads.

[0004] The patent application with application publication number CN107573777A discloses a hot melt road marking paint and a preparation method thereof, wherein the primer coating, the intermediate coating and the surface coating of the paint are combined with multiple functional additives to improve the wear resistance, crack resistance, corrosion resistance and antifouling performance. However, the road marking paint needs to be laid in multiple layers during laying, and the construction is relatively cumbersome. Summary of the invention

[0005] The object of the present invention is to provide a long-life road marking paint and a preparation method and application thereof, so as to solve the problem of poor wear resistance of the road marking paint.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A long-life road marking paint comprises the following raw materials in parts by weight: 18-20 parts of organosilicon hybrid polylactic acid modified C5 petroleum resin, 5-6 parts of pigment, 52-53 parts of filler, 22-25 parts of glass microspheres and 2.5-3 parts of additives.

[0008] Further, the pigment is one or more of titanium dioxide, chrome yellow, carbon black and phthalocyanine blue mixed in any proportion;

[0009] The filler is a mixture of quartz sand and heavy calcium carbonate, and the mass ratio of quartz sand to heavy calcium carbonate is 2:1;

[0010] The auxiliary agent is a mixture of dioctyl phthalate and polyethylene wax in a mass ratio of 1:1.5.

[0011] Dioctyl phthalate can improve the fluidity of the coating and the flexibility of the coating. However, excessive addition will reduce the viscosity of the coating, thereby reducing the stain resistance and durability. Polyethylene wax has excellent cold resistance, heat resistance and chemical resistance, and can play a role in internal lubrication and improve the wear resistance of the coating.

[0012] Furthermore, the organosilicon hybrid polylactic acid modified C5 petroleum resin is prepared by the following steps:

[0013] C5 petroleum resin and xylene are mixed, and under nitrogen protection, an initiator and organosilicon hybrid polylactic acid are added, and the reaction is carried out for 5-6 hours to obtain organosilicon hybrid polylactic acid modified C5 petroleum resin.

[0014] Furthermore, the mass ratio of the C5 petroleum resin to the organosilicon hybrid polylactic acid is 10:0.8-1.

[0015] Further, the initiator is benzoyl peroxide;

[0016] The mass ratio of the C5 petroleum resin to the initiator is 10:0.08.

[0017] Furthermore, the organosilicon hybrid polylactic acid is prepared by the following steps:

[0018] Step S1, under nitrogen protection conditions, adding a silicon-containing active diamine monomer and a dibasic anhydride monomer to N-methylpyrrolidone to carry out an imidization reaction to obtain an amino-terminated organosilicon hybrid modifier;

[0019] Step S2, adding the amino-terminated organosilicon hybrid modifier and lactide into dichloromethane, adding a tin catalyst, setting the temperature to 140° C., reacting for 24 hours under nitrogen protection, and vacuum drying at 40° C. to obtain organosilicon hybrid polylactic acid.

[0020] Further, the molar ratio of the silicon-containing active diamine monomer to the dibasic anhydride monomer in step S1 is 2-2.1:1;

[0021] In step S2, the mass ratio of the amino-terminated organosilicon hybrid modifier to lactide is 1-1.2:1; and the added amount of the tin catalyst is 0.5% of the mass of lactide.

[0022] Further, the silicon-containing active diamine monomer is 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane;

[0023] The dibasic anhydride monomers are pyromellitic dianhydride, 4,4-biphenyltetracarboxylic dianhydride, 4,4-biphenyl ether dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride;

[0024] The tin catalyst is one of stannous octoate and stannous chloride.

[0025] A method for preparing a long-life road marking paint comprises the following steps:

[0026] The raw materials are weighed according to weight parts, and the organosilicon hybrid polylactic acid modified C5 petroleum resin, pigment, filler, glass microbeads and additives are mixed evenly, and continuously heated at 180-220° C. to a molten state, stirred evenly, cooled and crushed to obtain a coating.

[0027] The invention discloses an application of a long-life marking paint in preparing road marking lines.

[0028] Beneficial effects of the present invention:

[0029] The invention prepares a road marking paint with good wear resistance and weather resistance; the preparation method of the invention is simple, adopts organosilicon hybrid polylactic acid modified C5 petroleum resin as a film-forming raw material, and introduces polar groups into the molecular structure of the C5 petroleum resin by using organosilicon hybrid polylactic acid, which can not only improve the adhesion effect of the road marking paint to the asphalt pavement and cement pavement, but also improve the wear resistance of the road marking paint through the grafting reaction of C5 petroleum resin and organosilicon hybrid polylactic acid, and in addition, consumes the unsaturated double bonds in the structure of the C5 petroleum resin through the grafting reaction, thereby improving the aging resistance of the road marking paint.

[0030] The organosilicon hybrid polylactic acid in the present invention is prepared by reacting an amino-terminated organosilicon hybrid modifier with lactide. The introduction of the imide segment and the SiO segment in the amino-terminated organosilicon hybrid modifier can not only improve the brittleness of conventional polylactic acid materials, but also reduce the influence of aging by utilizing the SiO bond having a bond energy greater than that of the CC bond, thereby improving the wear resistance and aging resistance of the hot-melt road marking paint, avoiding road marking cracking to a great extent, and improving the low-temperature resistance of the road marking paint, thereby increasing the service life of the road marking paint. DETAILED DESCRIPTION

[0031] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0032] Example 1

[0033] The preparation of organosilicon hybrid polylactic acid comprises the following steps:

[0034] Step S1, under nitrogen protection conditions, add silicon-containing active diamine monomer (1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane) and dibasic anhydride monomer (pyromellitic dianhydride) to N-methylpyrrolidone for imidization reaction, set the temperature to 0-5°C, stir and react for 12 hours; heat to 150°C, react for 1 hour; heat to 180°C, react for 2 hours, heat to 210°C, react for 2 hours, first dissolve with dichloromethane, then purify with dichloromethane-ether, and dry to obtain an amino-terminated organosilicon hybrid modifier; the molar ratio of silicon-containing active diamine monomer to dibasic anhydride monomer is 2.1:1;

[0035] Step S2, adding the amino-terminated organosilicon hybrid modifier and lactide to dichloromethane, adding stannous octoate, setting the temperature to 140°C, reacting for 24 hours under nitrogen protection, and vacuum drying at 40°C to obtain organosilicon hybrid polylactic acid. The mass ratio of the amino-terminated organosilicon hybrid modifier to lactide is 1:1. The amount of stannous octoate added is 0.5% of the mass of lactide.

[0036] Example 2

[0037] The preparation of organosilicon hybrid polylactic acid comprises the following steps:

[0038] Step S1, under nitrogen protection conditions, adding silicon-containing active diamine monomer (1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane) and dibasic anhydride monomer (4,4-biphenyl ether dianhydride) to N-methylpyrrolidone for imidization reaction, setting the temperature to 0-5°C, stirring the reaction for 12 hours; heating to 150°C, reacting for 1 hour; heating to 180°C, reacting for 2 hours, heating to 210°C, reacting for 2 hours, first dissolving with dichloromethane, then purifying with dichloromethane-ether, and drying to obtain an amino-terminated organosilicon hybrid modifier; the molar ratio of the silicon-containing active diamine monomer to the dibasic anhydride monomer is 2:1;

[0039] Step S2, adding the amino-terminated organosilicon hybrid modifier and lactide to dichloromethane, adding stannous octoate, setting the temperature to 140°C, reacting for 24 hours under nitrogen protection, and vacuum drying at 40°C to obtain organosilicon hybrid polylactic acid. The mass ratio of the amino-terminated organosilicon hybrid modifier to lactide is 1.2:1. The amount of stannous octoate added is 0.5% of the mass of lactide.

[0040] Example 3

[0041] Compared with Example 1, the dibasic anhydride monomer in this example is replaced by 4,4-biphenyltetracarboxylic dianhydride, and the other raw materials and preparation process are the same as those in Example 2.

[0042] Example 4

[0043] Compared with Example 1, the dibasic anhydride monomer in this example is replaced by 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and the other raw materials and preparation process are the same as those in Example 2.

[0044] Example 5

[0045] A method for preparing a long-life road marking paint comprises the following steps:

[0046] The first step is to mix C5 petroleum resin and xylene, add benzoyl peroxide and the organosilicon hybrid polylactic acid prepared in Example 1 under nitrogen protection, and react for 5-6 hours. After the reaction, add acetone until the precipitated white insoluble matter no longer increases, then filter and wash with acetone, dissolve the obtained solid in xylene, filter out the insoluble matter, wash with acetone, and dry at 70°C to constant weight to obtain organosilicon hybrid polylactic acid modified C5 petroleum resin; the mass ratio of C5 petroleum resin to benzoyl peroxide is 10:0.08; the mass ratio of C5 petroleum resin to organosilicon hybrid polylactic acid is 10:0.8-1.

[0047] Step 2: Weigh the raw materials by weight, mix 18-20 parts of organosilicon hybrid polylactic acid modified C5 petroleum resin, 5-6 parts of titanium dioxide, 52-53 parts of filler, 22-25 parts of glass microspheres, and 2.5-3 parts of additives, heat continuously at 180-220°C until molten, stir evenly, cool and crush to obtain the coating. The filler is a mixture of quartz sand and heavy calcium carbonate, the mass ratio of quartz sand and heavy calcium carbonate is 2:1; the additive is a mixture of dioctyl phthalate and polyethylene wax at a mass ratio of 1:1.5.

[0048] Referring to Table 1 below, the mass ratio of C5 petroleum resin and organosilicon hybrid polylactic acid and the amount of raw materials in the hot melt coating for road marking were adjusted, and the coating performance was tested. The results are shown in Table 1 below:

[0049] Table 1

[0050]

[0051]

[0052] Example 6

[0053] Compared with Sample 1 in Example 5, in this example, the organosilicon hybrid polylactic acid is replaced with the organosilicon hybrid polylactic acid prepared in Example 2 to obtain Sample 6.

[0054] Example 7

[0055] Compared with Sample 1 in Example 5, in this example, the organosilicon hybrid polylactic acid is replaced with the organosilicon hybrid polylactic acid prepared in Example 3 to obtain Sample 7.

[0056] Example 8

[0057] Compared with Sample 1 in Example 5, in this example, the organosilicon hybrid polylactic acid is replaced with the organosilicon hybrid polylactic acid prepared in Example 4 to obtain Sample 8.

[0058] Comparative Example 1

[0059] Compared with Sample 1 in Example 5, this comparative example replaces the organosilicon hybrid polylactic acid with untreated polylactic acid, and the treated C5 petroleum resin is used as a raw material to prepare Sample 9. The polylactic acid is prepared by the following steps: lactide is added to dichloromethane, stannous octoate is added, the temperature is set to 140°C, under nitrogen protection, the reaction is carried out for 24 hours, and vacuum drying is carried out at 40°C to obtain polylactic acid. The mass ratio of the amino-terminated organosilicon hybrid modifier to lactide is 1:1. The amount of stannous octoate added is 0.5% of the mass of lactide.

[0060] Comparative Example 2

[0061] In this comparative example, compared with Sample 1 in Example 5, the modified C5 petroleum resin is replaced with unmodified C5 petroleum resin to obtain Sample 10.

[0062] The prepared samples were tested with reference to "Road Marking Paint" JT / T280-2022 to test wear resistance, weather resistance and softening point. The test results are shown in Table 2 below:

[0063] Table 2

[0064]

[0065] The test results show that the road marking paint prepared by the present invention has good wear resistance and weather resistance, and no cracking, powdering or the like occurs after artificial accelerated aging.

[0066] The low temperature resistance of samples 3, 9 and 10 was tested. The initial marking paint was tested for low temperature crack resistance in accordance with the JT / T280-2022 specification for road marking paint. The specification requires a cycle of keeping at -10°C for 4 hours and leaving at room temperature for 4 hours. No cracking occurred after nine cycles. A small beam of marking paint was prepared according to the proportions of samples 3, 9 and 10. After keeping at -10°C for 4 hours, a low temperature bending test was carried out. The beam size was 170×23×20mm, the span was 120mm, the test temperature was -10°C, and the loading rate was 5mm / min. The results are shown in Table 3 below:

[0067] Table 3

[0068]

[0069] It can be seen from the test results that the coating of the present invention has good low temperature resistance.

[0070] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0071] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A long-life road marking paint, characterized in that: The method comprises the following raw materials in parts by weight: 18-20 parts of organosilicon hybrid polylactic acid modified C5 petroleum resin, 5-6 parts of pigment, 52-53 parts of filler, 22-25 parts of glass microbeads, and 2.5-3 parts of additives; The organosilicon hybrid polylactic acid modified C5 petroleum resin is prepared by the following steps: Step S1, under nitrogen protection conditions, adding a silicon-containing active diamine monomer and a dibasic anhydride monomer to N-methylpyrrolidone to carry out an imidization reaction to obtain an amino-terminated organosilicon hybrid modifier; Step S2, adding an amino-terminated organosilicon hybrid modifier and lactide to dichloromethane, adding a tin catalyst, setting the temperature to 140°C, reacting for 24 hours under nitrogen protection conditions, and vacuum drying at 40°C to obtain organosilicon hybrid polylactic acid; mixing C5 petroleum resin and xylene, adding an initiator and organosilicon hybrid polylactic acid under nitrogen protection conditions, reacting for 5-6 hours, and obtaining organosilicon hybrid polylactic acid modified C5 petroleum resin.

2. A long-life road marking paint according to claim 1, characterized in that: The pigment is one or more of titanium dioxide, chrome yellow, carbon black and phthalocyanine blue mixed in any proportion; The filler is a mixture of quartz sand and heavy calcium carbonate, and the mass ratio of quartz sand to heavy calcium carbonate is 2:1; The auxiliary agent is a mixture of dioctyl phthalate and polyethylene wax in a mass ratio of 1:1.

5.

3. The long-life road marking paint according to claim 1, characterized in that: The mass ratio of the C5 petroleum resin to the organosilicon hybrid polylactic acid is 10:0.8-1.

4. The long-life road marking paint according to claim 1, characterized in that: The initiator is benzoyl peroxide; The mass ratio of the C5 petroleum resin to the initiator is 10:0.

08.

5. The long-life road marking paint according to claim 1, characterized in that: The molar ratio of the silicon-containing active diamine monomer to the dibasic anhydride monomer in step S1 is 2-2.1:1; In step S2, the mass ratio of the amino-terminated organosilicon hybrid modifier to lactide is 1-1.2:1; and the added amount of the tin catalyst is 0.5% of the mass of lactide.

6. The long-life road marking paint according to claim 1, characterized in that: The silicon-containing active diamine monomer is 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane; The dibasic anhydride monomers are pyromellitic dianhydride, 4,4-biphenyltetracarboxylic dianhydride, 4,4-biphenyl ether dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride; The tin catalyst is one of stannous octoate and stannous chloride.

7. A method for preparing a long-life road marking paint according to any one of claims 1 to 6, characterized in that: The steps include: The raw materials are weighed according to weight parts, and the organosilicon hybrid polylactic acid modified C5 petroleum resin, pigment, filler, glass microbeads and additives are mixed evenly, and continuously heated at 180-220° C. to a molten state, stirred evenly, cooled and crushed to obtain a coating.

8. Use of the long-life marking paint according to any one of claims 1 to 6 in preparing road marking lines.

Images