A luminous film material and preparation method thereof

Abstract

The invention relates to the technical field of polymer materials, and discloses a luminous film material and a preparation method thereof. The luminous film material uses polypropylene as a base material, and uses functional hollow glass microbeads and an antifouling agent as main auxiliary agents. By improving the functionality of the hollow glass microbeads, the problem of the dispersibility of the hollow glass microbeads in the polypropylene base is solved, and the tensile strength and toughness of the polypropylene material are improved. The addition of the antifouling agent gives the polypropylene material waterproof, antifouling and self-cleaning properties, which can effectively avoid the attachment of stains and reduce the influence of stains on the reflective effect of the hollow glass microbeads. Therefore, the luminous film material prepared by the invention has excellent mechanical properties and antifouling properties, and can have an excellent reflective effect while keeping clean and not easy to be damaged.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a luminous film material and a preparation method thereof. Background Art

[0002] Luminous film can reflect light at night and is often used in landscape layout, interior decoration and other scenes. It can be made of polyethylene, polystyrene, polypropylene, polylactic acid and other materials. Polypropylene material is light in weight, heat-resistant, electrical insulating, environmentally friendly and non-toxic, has excellent barrier properties and chemical stability, can resist the erosion and penetration of oil, moisture, acid and alkali and other chemical substances, and is reliable in application; and the film made of polypropylene material has gloss and high transparency, can maintain a high light transmittance, improve the reflective effect, make the polypropylene film more outstanding in visual effect, can provide better aesthetics and decorativeness; in addition, polypropylene material has good processing performance and can be easily processed into film materials of different shapes and sizes according to different needs. Therefore, polypropylene can be used as a luminous film material.

[0003] However, polypropylene still has some shortcomings as a material for making luminous film. For example, the tensile strength and toughness of polypropylene are poor, and it is easy to be damaged when subjected to external force; the anti-fouling performance of polypropylene material is insufficient, and when the polypropylene luminous film is pasted on the wall or glass of the room, it is easy to be stained, affecting the reflective effect, limiting the application of polypropylene in luminous film materials. Therefore, it is necessary to improve polypropylene so that the prepared luminous film can meet the use requirements of different environments.

[0004] Hollow glass microspheres have the characteristics of spherical lenses and can converge light, so that parallel light converges at a point outside the spherical surface after passing through the glass microspheres, realizing light reflection and having a reflective effect. In addition, hollow glass microspheres are hard and uniform, and are good reinforcing materials. When added to polypropylene materials, they can be prepared into luminous film materials, which have a reflective effect at night. However, directly adding hollow glass microspheres to polypropylene materials will cause the hollow glass microspheres to be unevenly distributed in the polypropylene matrix and agglomerate, thereby affecting the overall performance of the polypropylene material. Therefore, the hollow glass microspheres need to be modified. Summary of the invention

[0005] The purpose of the present invention is to provide a luminous film material and a preparation method thereof, which solves the following technical problems:

[0006] (1) Solved the dispersibility problem of hollow glass microspheres in polypropylene materials;

[0007] (2) Solved the problem of poor mechanical properties of polypropylene materials;

[0008] (3) The problem of poor antifouling performance of polypropylene materials has been solved.

[0009] The purpose of the present invention can be achieved through the following technical solutions:

[0010] A luminous film material comprises the following raw materials in parts by weight: 60-80 parts of polypropylene, 4-8 parts of functional hollow glass microspheres, 2-4 parts of antifouling agent, 1-3 parts of cross-linking agent, 0.5-1.5 parts of lubricant, and 0.4-0.8 parts of antioxidant.

[0011] Furthermore, the method for preparing the functional hollow glass microspheres comprises the following steps:

[0012] Step A, after adjusting the pH value of the tris(hydroxymethyl)aminomethane) solution with a hydrochloric acid solution, adding dopamine and stirring to dissolve, then adding hollow glass microspheres ultrasonically washed with anhydrous ethanol, and after uniform dispersion, heating to 40-60° C., adjusting the stirring rate to 50-100 r / min, reacting for 2-4 hours, filtering and drying to obtain modified hollow glass microspheres;

[0013] Step B: Add the modified hollow glass microspheres to toluene, disperse them evenly, introduce nitrogen, add carboxyl-terminated polybutadiene liquid rubber, 4-dimethylaminopyridine and N,N-dicyclohexylcarbodiimide, heat to 55-65° C., stir and react for 2-4 hours to obtain functional hollow glass microspheres.

[0014] By adopting the above technical scheme, hollow glass microspheres are chemically modified with dopamine to obtain modified hollow glass microspheres with active amino groups. Under the action of a catalyst, the active amino groups in the modified hollow glass microspheres can react with the active carboxyl groups in the carboxyl-terminated polybutadiene liquid rubber to obtain functional hollow glass microspheres.

[0015] Furthermore, in step A, the pH value is 8-9.

[0016] Furthermore, in step A, the particle size of the hollow glass microspheres is 10-20 μm.

[0017] Furthermore, in step B, the carboxyl value of the carboxyl-terminated polybutadiene liquid rubber is 0.43-0.52 mmol / g.

[0018] Furthermore, the preparation method of the antifouling agent is as follows:

[0019] Add hydrogen-containing fluorosilicone oil to toluene, stir until dissolved, introduce nitrogen, add tert-butyl acrylate, stir for 10-15 minutes, heat to 70-80°C, add platinum catalyst, keep warm for 3-4 hours, distill under reduced pressure, cool, and obtain an antifouling agent.

[0020] By adopting the above technical scheme, the active hydrogen in the hydrogen-containing fluorosilicone oil and the unsaturated olefin in the structure of tert-butyl acrylate can undergo addition reaction under the action of a platinum catalyst to obtain an antifouling agent.

[0021] Furthermore, the hydrogen content of the hydrogen-containing fluorosilicone oil is 0.2-1%.

[0022] Furthermore, the crosslinking agent is dicumyl peroxide and styrene; the lubricant is polyethylene wax or magnesium stearate; and the antioxidant is pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) and tris(2,4-di-tert-butylphenyl)phosphite.

[0023] A method for preparing a luminous film material comprises the following steps:

[0024] Step 1: Add polypropylene, functional hollow glass microspheres, antifouling agent, crosslinking agent, lubricant, and antioxidant into a mixer according to weight and mix evenly to obtain a mixed material;

[0025] Step 2: Add the mixed material into a twin-screw extruder, melt blend at 180-200° C., extrude, granulate, and dry to obtain a luminous film material.

[0026] Furthermore, in step 1, the rotation speed of the mixer is set to 100-200 r / min, and the mixing time is 15-30 min.

[0027] Beneficial effects of the present invention:

[0028] (1) The present invention prepares hollow glass microbeads with surface modified with polybutadiene macromolecules as additives. Due to the presence of polybutadiene molecular chains, a "transition" structure is formed between the hollow glass microbeads and the polypropylene matrix, which can effectively improve the compatibility between the two and enable the hollow glass microbeads to be evenly dispersed in the polypropylene. Therefore, the advantages of the hollow glass microbeads can be efficiently utilized to improve the tensile strength and other mechanical properties of the film. In addition, the evenly dispersed hollow glass microbeads can evenly reflect the incident light, thereby achieving an excellent reflective effect. The functional hollow glass microbeads can be cross-linked with the polypropylene material under the action of a cross-linking agent to form a network structure, which firmly fixes the hollow glass microbeads in the polypropylene material, avoiding the problem of the hollow glass microbeads falling off and causing the reflective effect to be weakened. At the same time, the polybutadiene molecular chain has a buffering effect, which can improve the toughness of the polypropylene material and make the luminous film not easily damaged.

[0029] (2) The antifouling agent prepared by the present invention has a highly hydrophobic tert-butyl group, a silicon-oxygen bond and a fluorine-containing group, and therefore has an extremely low surface energy. A small amount of addition can make the polypropylene material produce a lotus leaf-like hydrophobic effect, effectively avoiding the adhesion of stains, protecting the surface of the polypropylene material from being bright and clean, and making the polypropylene material waterproof, antifouling and self-cleaning. This prevents stains from affecting the reflective effect of the hollow glass microbeads, reduces the number of cleaning and maintenance times, and thus extends the service life of the luminous film.

[0030] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0032] Figure 1 The infrared spectra of the antifouling agent and the hydrogen fluorosilicone oil prepared in the examples of the present invention are shown. DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in 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. Example 1

[0034] 1. Preparation of functional hollow glass microspheres

[0035] Step A, after adjusting the pH value of 100 mL of 1.2 g / L tris(hydroxymethyl)aminomethane) solution to 8.5 with 1 mol / L hydrochloric acid solution, add 0.25 g of dopamine and stir to dissolve, then add 2.3 g of 15 μm hollow glass microspheres ultrasonically washed with anhydrous ethanol, disperse evenly, heat to 50° C., adjust the stirring rate to 80 r / min, react for 3 h, filter and dry to obtain modified hollow glass microspheres;

[0036] Step B: Add 2 g of modified hollow glass microspheres to toluene, disperse evenly, introduce nitrogen, add 2.8 g of carboxyl-terminated polybutadiene liquid rubber with a carboxyl value of 0.45 mmol / g, 0.3 g of 4-dimethylaminopyridine and 0.5 g of N,N-dicyclohexylcarbodiimide, heat to 60° C., stir and react for 3 h to obtain functional hollow glass microspheres.

[0037] The titration method was used to determine the amino content in the modified hollow glass microspheres and functional hollow glass microspheres. 0.3 g of the modified hollow glass microspheres and 0.3 g of the functional hollow glass microspheres were taken respectively, added to 20 mL of glacial acetic acid, 200 mL of deionized water, 1 g of potassium bromide, and 30 mL of 6 mol / L hydrochloric acid solution. At 5 ° C, 0.1 mol / L sodium nitrite standard solution was used to make the starch potassium iodide test paper turn blue and do not change color within five minutes. Then, the addition of sodium nitrite solution can be stopped. The calculation formula for the amino content is: W = (MCV / 1000m)×100%, where W represents the amino content (%), M represents the molecular weight of the sample, C represents the concentration of the sodium nitrite standard solution (mol / L), V represents the volume of the consumed sodium nitrite standard solution (mL), and m represents the mass of the sample (g). The amino content in the modified hollow glass microspheres is 8.2%, and the amino content in the functional hollow glass microspheres is 2.3%. The decrease in the amino content is because the amino groups in the modified hollow glass microspheres react with the carboxyl groups in the carboxyl-terminated polybutadiene liquid rubber structure, consuming the amino groups.

[0038] 2. Preparation of antifouling agent

[0039] Take 2.8g of hydrogen-containing fluorosilicone oil with a hydrogen content of 0.8% and add it to toluene. After stirring until dissolved, introduce nitrogen, add 1.8g of tert-butyl acrylate, stir for 10 minutes, heat to 75°C, add 10μg of platinum catalyst, keep the reaction warm for 4 hours, distill under reduced pressure, cool, and obtain an antifouling agent.

[0040] The potassium bromide tablet method was used to prepare the sample, and the hydrogen fluorine silicone oil and antifouling agent were tested by infrared spectrometer. Figure 1 As shown, the spectral wavenumber test range is 4000cm-1-500cm-1. Analysis shows that in the infrared spectrum of hydrogen-fluorosilicone oil, the absorption peak of methylene appears at 2931cm-1, the absorption peak of silicon-hydrogen bond appears at 2131cm-1, and the absorption peak of silicon-oxygen bond appears at 1025cm-1. In the infrared spectrum of the antifouling agent, the absorption peak of silicon-hydrogen bond at 2131cm-1 disappears, the absorption peak of ester group appears at 1730cm-1, and the absorption peak of tert-butyl group appears at 1367cm-1.

[0041] 3. Preparation of luminous film materials

[0042] Step 1: Add 60g polypropylene, 4g functional hollow glass microspheres, 2g antifouling agent, 0.5g diisopropylbenzene peroxide, 1g styrene, 0.5g magnesium stearate, 0.2g pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) and 0.2g tris(2,4-di-tert-butylphenyl)phosphite into a mixer and mix evenly. The speed of the mixer is set to 100r / min and the mixing time is 15min. A mixed material is obtained;

[0043] Step 2: Add the mixed material into a twin-screw extruder, melt blend at 180° C., extrude, granulate, and dry to obtain a luminous film material. Example 2

[0044] Preparation of luminous film materials

[0045] Step 1: Add 70g polypropylene, 6g functional hollow glass microspheres, 3g antifouling agent, 0.5g diisopropylbenzene peroxide, 2g styrene, 1g magnesium stearate, 0.3g pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) and 0.3g tris(2,4-di-tert-butylphenyl)phosphite into a mixer and mix evenly. The speed of the mixer is set to 150r / min and the mixing time is 20min. A mixed material is obtained;

[0046] Step 2: Add the mixed material into a twin-screw extruder, melt blend at 190° C., extrude, granulate, and dry to obtain a luminous film material.

[0047] The preparation method of the functional hollow glass microspheres and the antifouling agent is the same as that in Example 1. Example 3

[0048] Preparation of luminous film materials

[0049] Step 1: Add 80g polypropylene, 8g functional hollow glass microspheres, 4g antifouling agent, 0.5g diisopropylbenzene peroxide, 2.5g styrene, 1.5g magnesium stearate, 0.4g pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) and 0.4g tris(2,4-di-tert-butylphenyl)phosphite into a mixer and mix evenly. The speed of the mixer is set to 200r / min and the mixing time is 30min. A mixed material is obtained;

[0050] Step 2: Add the mixed material into a twin-screw extruder, melt blend at 200° C., extrude, granulate, and dry to obtain a luminous film material.

[0051] The preparation method of the functional hollow glass microspheres and the antifouling agent is the same as that in Example 1.

[0052] Comparative Example 1

[0053] Preparation of luminous film materials

[0054] Step 1: Add 70g polypropylene, 6g functional hollow glass microspheres, 0.5g diisopropylbenzene peroxide, 2g styrene, 1g magnesium stearate, 0.3g pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) and 0.3g tris(2,4-di-tert-butylphenyl)phosphite into a mixer and mix evenly. The speed of the mixer is set to 150r / min and the mixing time is 20min. A mixed material is obtained;

[0055] Step 2: Add the mixed material into a twin-screw extruder, melt blend at 190° C., extrude, granulate, and dry to obtain a luminous film material.

[0056] The preparation method of the functional hollow glass microspheres is the same as that in Example 1.

[0057] Comparative Example 2

[0058] Preparation of luminous film materials

[0059] Step 1: Add 70g polypropylene, 6g functional hollow glass microspheres, 3g hydrogen-containing fluorosilicone oil, 0.5g diisopropylbenzene peroxide, 2g styrene, 1g magnesium stearate, 0.3g pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) and 0.3g tris(2,4-di-tert-butylphenyl)phosphite into a mixer and mix evenly. The mixer speed is set to 150r / min and the mixing time is 20min. A mixed material is obtained;

[0060] Step 2: Add the mixed material into a twin-screw extruder, melt blend at 190° C., extrude, granulate, and dry to obtain a luminous film material.

[0061] The preparation method of the functional hollow glass microspheres is the same as that in Example 1.

[0062] Comparative Example 3

[0063] Preparation of luminous film materials

[0064] Step 1: Add 70g polypropylene, 6g hollow glass microspheres, 3g antifouling agent, 0.5g diisopropylbenzene peroxide, 2g styrene, 1g magnesium stearate, 0.3g pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) and 0.3g tris(2,4-di-tert-butylphenyl)phosphite into a mixer and mix evenly. The speed of the mixer is set to 150r / min and the mixing time is 20min. A mixed material is obtained;

[0065] Step 2: Add the mixed material into a twin-screw extruder, melt blend at 190° C., extrude, granulate, and dry to obtain a luminous film material.

[0066] The preparation method of the antifouling agent is the same as that of Example 1.

[0067] Performance Testing

[0068] Performance test of the luminous film materials prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 3:

[0069] The luminous film materials prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were made into film samples that met the test standards. The tensile strength and elongation at break of the samples were tested according to GB / T 1040.3-2006 standard to determine the mechanical properties and toughness. The contact angle of the sample surface was measured using a German DAtaphysics OCA25 contact angle measuring instrument at room temperature. The water droplet used was 2.0 μL. The contact angle of the sample was measured 5 times, and the average value was taken to determine the antifouling performance of the sample. The test results are shown in the following table:

[0070]

[0071] It can be seen from the above table that the luminous films prepared by Examples 1 to 3 of the present invention have excellent tensile strength, toughness and anti-fouling properties, among which Example 2 has the best test effect. Comparative Example 1 does not add an anti-fouling agent, and cannot utilize the effect of the hydrogen-containing fluorosilicone oil grafted with a strong hydrophobic tert-butyl group to prevent stains from adhering to the luminous film, so that the luminous film has a self-cleaning effect, so the contact angle test result is poor. Comparative Example 2 adds hydrogen-containing fluorosilicone oil, which has a certain hydrophobic and anti-fouling effect, but does not graft a tert-butyl group with a strong hydrophobic effect, so the contact angle test result is poor. Comparative Example 3 adds hollow glass microbeads that have not been functionally modified, and the tensile strength and toughness are poor. It may be that the poor dispersibility of the hollow glass microbeads in the polypropylene material leads to agglomeration, which affects the overall strength of the luminous film, and it is impossible to use polybutadiene rubber to improve the toughness of the luminous film.

[0072] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A luminous film material, characterized in that: The invention comprises the following raw materials in parts by weight: 60-80 parts of polypropylene, 4-8 parts of functional hollow glass microspheres, 2-4 parts of antifouling agent, 1-3 parts of crosslinking agent, 0.5-1.5 parts of lubricant, and 0.4-0.8 parts of antioxidant; The method for preparing the functional hollow glass microspheres comprises the following steps: Step A, after adjusting the pH value of the tris(hydroxymethyl)aminomethane) solution with a hydrochloric acid solution, adding dopamine and stirring to dissolve, then adding hollow glass microspheres ultrasonically washed with anhydrous ethanol, and after uniform dispersion, heating to 40-60° C., adjusting the stirring rate to 50-100 r / min, reacting for 2-4 hours, filtering and drying to obtain modified hollow glass microspheres; Step B, adding the modified hollow glass microspheres to toluene, dispersing them uniformly, introducing nitrogen, adding carboxyl-terminated polybutadiene liquid rubber, 4-dimethylaminopyridine and N,N-dicyclohexylcarbodiimide, heating to 55-65° C., stirring and reacting for 2-4 hours, and obtaining functional hollow glass microspheres; The preparation method of the antifouling agent is as follows: Add hydrogen-containing fluorosilicone oil to toluene, stir until dissolved, introduce nitrogen, add tert-butyl acrylate, stir for 10-15 minutes, heat to 70-80°C, add platinum catalyst, keep warm for 3-4 hours, distill under reduced pressure, cool, and obtain an antifouling agent.

2. A luminous film material according to claim 1, characterized in that: In step A, the pH value is 8-9.

3. The luminous film material according to claim 1, characterized in that: In step A, the particle size of the hollow glass microspheres is 10-20 μm.

4. The luminous film material according to claim 1, characterized in that: In step B, the carboxyl value of the carboxyl-terminated polybutadiene liquid rubber is 0.43-0.52 mmol / g.

5. The luminous film material according to claim 1, characterized in that: The hydrogen content of the hydrogen-containing fluorosilicone oil is 0.2-1%.

6. The luminous film material according to claim 1, characterized in that: The crosslinking agent is dicumyl peroxide and styrene; the lubricant is polyethylene wax or magnesium stearate; and the antioxidant is pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid)ester and tris(2,4-di-tert-butylphenyl)phosphite.

7. A method for preparing the luminous film material according to claim 1, characterized in that: The following steps are involved: Step 1, adding polypropylene, functional hollow glass microspheres, antifouling agent, crosslinking agent, lubricant, and antioxidant into a mixer according to weight parts and mixing evenly to obtain a mixed material; Step 2: Add the mixed material into a twin-screw extruder, melt blend at 180-200° C., extrude, granulate, and dry to obtain a luminous film material.

8. The method for preparing a luminous film material according to claim 7, characterized in that: In step 1, the speed of the mixer is set to 100-200 r / min, and the mixing time is 15-30 min.

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