Functional material for anti-aging outdoor seat and preparation method of functional material

Abstract

The invention relates to the technical field of materials, and discloses an anti-aging functional material for outdoor seats and a preparation method thereof.The functional material is prepared by taking polyethylene as a base material and taking a diatomite functional material and the like as an additive through mixing and extrusion granulation processes. Wherein the diatomite functional material is prepared by modifying a macromolecular substance with a perylene bisimide and benzophenone alternate connection structure on the surface of diatomite, and the compatibility between the diatomite and polyethylene can be effectively improved due to the existence of the macromolecular substance, so that the diatomite can exert the enhancement advantage of serving as an inorganic additive; the mechanical property of the material is improved, a benzophenone ultraviolet absorption functional group in a macromolecular substance structure can endow the material with an excellent anti-ultraviolet aging effect, so that the material can keep the anti-ultraviolet aging effect for a long time, and due to existence of a rigid heterocyclic structure of perylene bisimide, the stability of the material is higher; further, good high-temperature resistance is shown.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and in particular to a functional material for anti-aging outdoor seats and a preparation method thereof. Background Art

[0002] As an important facility in public spaces and leisure places, the material selection of outdoor chairs is crucial. Polyethylene has the advantages of being light, wear-resistant, waterproof, corrosion-resistant, and cold-resistant. Among them, the light weight and wear-resistant characteristics can meet the use needs of outdoor chairs that need to be moved frequently. Not only are they light and easy to carry, but they can also prevent wear caused by frequent movement. The waterproof and corrosion-resistant characteristics can effectively resist the erosion of rain, humid environments, and chemicals, and can reduce the frequency of replacement due to corrosion and damage. In addition, the cold-resistant characteristics can also meet the use needs of relatively extreme environments. Based on the above characteristics, polyethylene is widely used in the production of outdoor chairs, and has shown characteristics such as durability, beautiful gloss, and easy cleaning. With increasing use, outdoor chairs made from polyethylene have also developed significant drawbacks, primarily poor resistance to UV aging, environmental stress cracking, and thermal insulation. These deficiencies have a significant negative impact on the service life of outdoor chairs, leading to modifications to polyethylene to improve its overall performance.

[0003] At present, polyethylene can be enhanced and modified by adding additives such as inorganic materials. However, there are obvious interface problems between the hydrophilic inorganic material itself and the lipophilic polyethylene matrix. The two are incompatible with each other, which can easily cause negative effects on the mechanical properties of the material. Therefore, the present invention provides a functional material based on polyethylene, which can solve the problems existing in the prior art. Summary of the Invention

[0004] In order to solve the problems mentioned in the background technology, the purpose of the present invention is to provide a functional material for anti-aging outdoor seats and a preparation method thereof.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A functional material for anti-aging outdoor chairs, comprising the following raw materials in parts by weight: 65-85 parts of polyethylene, 5-15 parts of compatibilizer, 3.5-6.5 parts of diatomaceous earth functional material, 1-5 parts of calcium carbonate whiskers, 0.5-1.5 parts of lubricant, 5-10 parts of toughening agent, 0.1-0.5 parts of antioxidant; The diatomite functional material is prepared by modifying the surface of diatomite with a macromolecular substance having an alternating connection structure of perylene imide and benzophenone.

[0006] As a further embodiment of the present invention, the preparation method of the diatomaceous earth functional material is as follows: Step 1: adding a halogen-containing silane coupling agent to purified water, hydrolyzing it at a temperature of 50-60° C. for 2-4 hours to form a hydrolyzate; dispersing the pretreated diatomaceous earth in ethanol to form a dispersion; slowly adding the hydrolyzate to the dispersion, raising the temperature to 60-70° C., stirring at this temperature for 4-8 hours, cooling and discharging the material to obtain the modified diatomaceous earth; Step 2: adding 3,4,9,10-tetracarboxylic acid diimide to anhydrous ethanol and stirring until a uniform mixture is formed, then adding a methanol aqueous solution of potassium hydroxide to the mixture, stirring at a temperature of 50-60° C. for 2-4 hours, filtering out the solid product, washing, and drying to obtain 3,4,9,10-tetracarboxylic acid diimide potassium salt; Step 3: Add the modified diatomaceous earth to toluene, and after ultrasonic dispersion, add the 3,4,9,10-tetracarboxylic diimide potassium salt bridging agent to the formed dispersion, then raise the temperature to 70-80°C, stir for 3-6 hours, and continue to add the halogenated ultraviolet absorber. After the addition, raise the temperature to 80-90°C, continue stirring, and carry out chain extension polymerization for 12-18 hours. Stop heating, filter out the solid product, wash, and vacuum dry to obtain the diatomaceous earth functional material.

[0007] As a further embodiment of the present invention, the halogen-containing silane coupling agent is any one of 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltrimethoxysilane or 3-bromopropyltriethoxysilane.

[0008] As a further embodiment of the present invention, the diatomaceous earth pretreatment method is: Add diatomaceous earth to nitric acid, disperse evenly, heat to 70-75°C, stir for 4-8 hours, then discharge, wash to neutrality, and vacuum dry.

[0009] As a further embodiment of the present invention, the preparation method of the halogenated ultraviolet absorber is as follows: Add ultraviolet absorber BP-2 and halogenated isocyanate in a molar ratio of 1:2 to N,N-dimethylformamide, start stirring, mix evenly, introduce nitrogen protection, continue to add tin catalyst, and after the addition is completed, increase the temperature to 70-80°C, keep the temperature under constant stirring for 6-9 hours, cool and discharge, and undergo purification treatment to obtain a halogenated ultraviolet absorber.

[0010] As a further embodiment of the present invention, the halogenated isocyanate is chloroethyl isocyanate or 3-chloropropyl isocyanate.

[0011] As a further embodiment of the present invention, the tin catalyst is any one of dibutyltin dilaurate, stannous octoate, and dibutyltin diacetate.

[0012] As a further embodiment of the present invention, the mass ratio of the 3,4,9,10-tetracarboxylic diimide potassium salt, the modified diatomaceous earth and the halogenated ultraviolet absorber is 3-5:1:2-3.

[0013] In the above technical solution, diatomaceous earth is first subjected to an acidification treatment to remove surface impurities, and then a halogen-containing silane coupling agent is used to modify its surface so that its surface carries halogen functional groups. Then, 3,4,9,10-tetracarboxylic diimide potassium salt is used as a bridging agent, one end of which is substituted with the halogen functional group on the surface of the diatomaceous earth, and the other end is connected with the halogen functional group in the structure of the halogenated ultraviolet absorber. By adding an excess of 3,4,9,10-tetracarboxylic diimide potassium salt and the halogenated ultraviolet absorber, the 3,4,9,10-tetracarboxylic diimide potassium salt and the halogenated ultraviolet absorber can be subjected to in-situ substitution polymerization on the surface of the diatomaceous earth to obtain a diatomaceous earth with a macromolecular substance modified with an alternating connection structure of perylene imide and benzophenone, that is, a diatomaceous earth functional material.

[0014] The halogenated UV absorber is made of UV absorber BP-2 and halogenated isocyanate as raw materials. Under the action of tin catalyst, the active hydroxyl groups and active isocyanate groups in each other's structures can undergo an amine esterification reaction. By controlling the molar ratio of the two, a halogenated UV absorber containing two equivalents of halogen substituents in the structure can be prepared.

[0015] As a further embodiment of the present invention, the compatibilizer is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene; the lubricant is polyethylene wax, liquid paraffin or montan wax; the toughening agent is methyl methacrylate-butadiene-styrene terpolymer; and the antioxidant is any one of antioxidant 1010, antioxidant 1076 or antioxidant 168.

[0016] A method for preparing a functional material for an anti-aging outdoor seat comprises the following steps: The first step is to add all the raw materials weighed according to their weight into a blender, control the speed to 800-1000r / min, and mechanically stir and mix for 1-2 hours to form a uniform premix; The second step is to feed the premix into a twin-screw extruder, set the temperature of each zone as follows: zone 1 190-200℃, zone 2 200-210℃, zone 3 210-220℃, zone 4 220-230℃, zone 5 210-220℃, and melt-extrude the premix. The obtained masterbatch is pelletized.

[0017] Beneficial effects of the present invention: The present invention modifies polyethylene by modifying the surface of diatomaceous earth with a macromolecular substance containing an alternating structure of perylene imide and benzophenone, using this substance as a diatomaceous earth functional material. The macromolecular substance forms a "transition" connecting layer between the diatomaceous earth and the polyethylene. This macromolecular substance exhibits lipophilicity, effectively improving their compatibility. Furthermore, the macromolecular substance can extend during the subsequent melt extrusion process, forming an entangled structure with the polyethylene molecular chains. This allows the diatomaceous earth to leverage its inherent strength as an inorganic additive, improving the material's mechanical properties.

[0018] In addition, the benzophenone UV-absorbing functional group in the macromolecular structure can give the material excellent anti-UV aging effects. Moreover, because it is confined to the surface of diatomaceous earth, it cannot easily volatilize and migrate, allowing the material to maintain long-term anti-UV aging effects. The presence of the rigid heterocyclic structure of perylene imide can make the material more stable, thereby exhibiting good high-temperature resistance.

[0019] 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

[0020] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0021] Figure 1 This is the infrared test image of the halogenated UV absorber. DETAILED DESCRIPTION

[0022] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. 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 making any creative efforts shall fall within the scope of protection of the present invention.

[0023] Example 1 A functional material for anti-aging outdoor chairs, comprising the following raw materials in parts by weight: 65 parts of polyethylene, 5 parts of maleic anhydride grafted polyethylene as a compatibilizer, 3.5 parts of diatomaceous earth functional material, 1 part of calcium carbonate whisker, 0.5 parts of lubricant polyethylene wax, 5 parts of toughening agent methyl methacrylate-butadiene-styrene terpolymer, 0.1 parts of antioxidant 1010; The preparation method of the functional material comprises the following steps: The first step is to add all the raw materials weighed according to their weight into a blender, control the speed to 800r / min, and mechanically stir and mix for 2h to form a uniform premix; The second step is to feed the premix into a twin-screw extruder, set the temperature of each zone as follows: zone 1 200℃, zone 2 210℃, zone 3 220℃, zone 4 230℃, zone 5 220℃, and melt-extrude the premix. The obtained masterbatch is pelletized.

[0024] Example 2 A functional material for anti-aging outdoor chairs, comprising the following raw materials in parts by weight: 70 parts of polyethylene, 10 parts of maleic anhydride grafted polyethylene as a compatibilizer, 6 parts of diatomaceous earth functional material, 3 parts of calcium carbonate whiskers, 1 part of lubricant polyethylene wax, 6 parts of toughening agent methyl methacrylate-butadiene-styrene terpolymer, 0.2 parts of antioxidant 1076; The preparation method of the functional material comprises the following steps: The first step is to add all the raw materials weighed according to their weight into a blender, control the speed to 1000r / min, and mechanically stir and mix for 1 hour to form a uniform premix; The second step is to feed the premix into a twin-screw extruder, set the temperature of each zone as follows: zone 1 200℃, zone 2 210℃, zone 3 220℃, zone 4 230℃, zone 5 220℃, and melt-extrude the premix. The obtained masterbatch is pelletized.

[0025] Example 3 A functional material for anti-aging outdoor chairs, comprising the following raw materials in parts by weight: 85 parts of polyethylene, 15 parts of maleic anhydride grafted polypropylene as a compatibilizer, 6.5 parts of diatomaceous earth functional material, 5 parts of calcium carbonate whiskers, 1.5 parts of lubricant polyethylene wax, 10 parts of toughening agent methyl methacrylate-butadiene-styrene terpolymer, 0.5 parts of antioxidant 168; The preparation method of the functional material comprises the following steps: The first step is to add all the raw materials weighed according to their weight into a blender, control the speed to 1000r / min, and mechanically stir and mix for 1 hour to form a uniform premix; The second step is to feed the premix into a twin-screw extruder, set the temperature of each zone as follows: zone 1 200℃, zone 2 210℃, zone 3 220℃, zone 4 230℃, zone 5 220℃, and melt-extrude the premix. The obtained masterbatch is pelletized.

[0026] The preparation method of the diatomaceous earth functional material in the above embodiment is as follows: Step S1: add 3 g of diatomaceous earth to 100 mL of 3 mol / L nitric acid, disperse evenly, heat to 70° C., stir for 6 h, then discharge, wash to neutrality, and vacuum dry. Step S2, adding 1.6 g of 3-chloropropyltriethoxysilane to 50 mL of purified water, hydrolyzing at 60° C. for 3 h to form a hydrolyzate; dispersing 2.5 g of pretreated diatomaceous earth in 80 mL of ethanol to form a dispersion; slowly adding the hydrolyzate to the dispersion, raising the temperature to 65° C., stirring at this temperature for 6 h, cooling and discharging the material to obtain modified diatomaceous earth; Step S3, adding 1.2 g of 3,4,9,10-tetracarboxylic diimide to 15 mL of anhydrous ethanol, stirring to form a uniform mixed solution, adding 0.5 g of potassium hydroxide to a composite solution of 5 mL of methanol and 1 mL of purified water, stirring evenly, and adding the mixture to the mixture, stirring at 55° C. for 3 h, filtering out the solid product, washing, and drying to obtain 3,4,9,10-tetracarboxylic diimide potassium salt; Step S4, adding 0.6 g of modified diatomaceous earth to toluene, ultrasonically dispersing it uniformly, then adding 2.5 g of 3,4,9,10-tetracarboxamide potassium salt bridging agent to the formed dispersion, then raising the temperature to 75 ° C., stirring for 3 hours, and then adding 1.5 g of halogenated UV absorber. After the addition, the temperature is raised to 85 ° C., stirring is continued, and chain extension polymerization is carried out for 16 hours. The heating is stopped, the solid product is filtered out, washed, and vacuum dried to obtain the diatomaceous earth functional material.

[0027] The preparation method of the halogenated ultraviolet absorber is as follows: 0.4 g of ultraviolet absorber BP-2 and 0.34 g of chloroethyl isocyanate were added to N, N-dimethylformamide, stirred, and after mixing evenly, nitrogen was introduced for protection. 0.01 g of dibutyltin dilaurate was added. After the addition was completed, the temperature was raised to 75 ° C. The mixture was kept warm for 8 hours under continuous stirring, and then the temperature was lowered and the material was discharged. After purification, a halogenated ultraviolet absorber was obtained.

[0028] Figure 1 This is the infrared analysis test chart of the halogenated UV absorber, where 3426cm -1 The characteristic absorption peak at 3298 cm is the NH characteristic absorption peak produced by the amine esterification reaction. -1 The characteristic absorption peak at 1737 cm is the characteristic absorption peak of the phenolic hydroxyl group in the benzophenone structure. -1 The characteristic absorption peak at 1708 cm is the C=O characteristic absorption peak in the benzophenone structure. -1 The characteristic absorption peak appearing at is the characteristic absorption peak of the amine ester group C=O produced by the amine esterification reaction.

[0029] Comparative Example 1 A functional material for anti-aging outdoor chairs, comprising the following raw materials in parts by weight: 70 parts of polyethylene, 10 parts of maleic anhydride grafted polyethylene as a compatibilizer, 6 parts of diatomaceous earth, 3 parts of calcium carbonate whiskers, 1 part of polyethylene wax as a lubricant, 6 parts of methyl methacrylate-butadiene-styrene terpolymer as a toughening agent, and 0.2 parts of antioxidant 1076; The preparation method of the functional material comprises the following steps: The first step is to add all the raw materials weighed according to their weight into a blender, control the speed to 1000r / min, and mechanically stir and mix for 1 hour to form a uniform premix; The second step is to feed the premix into a twin-screw extruder, set the temperature of each zone as follows: zone 1 200℃, zone 2 210℃, zone 3 220℃, zone 4 230℃, zone 5 220℃, and melt-extrude the premix. The obtained masterbatch is pelletized.

[0030] Comparative Example 2 A functional material for anti-aging outdoor chairs, comprising the following raw materials in parts by weight: 70 parts of polyethylene, 10 parts of maleic anhydride grafted polyethylene as a compatibilizer, 3 parts of calcium carbonate whiskers, 1 part of polyethylene wax as a lubricant, 6 parts of methyl methacrylate-butadiene-styrene terpolymer as a toughening agent, and 0.2 parts of antioxidant 1076; The preparation method of the functional material comprises the following steps: The first step is to add all the raw materials weighed according to their weight into a blender, control the speed to 1000r / min, and mechanically stir and mix for 1 hour to form a uniform premix; The second step is to feed the premix into a twin-screw extruder, set the temperature of each zone as follows: zone 1 200℃, zone 2 210℃, zone 3 220℃, zone 4 230℃, zone 5 220℃, and melt-extrude the premix. The obtained masterbatch is pelletized.

[0031] Performance Testing The materials in the examples and comparative examples were made into test specimens, and various performance tests were performed. The test results are recorded in the following table: The tensile strength was tested according to the standard GB / T 1040.1-2018, with the tensile rate set at 100 mm / min. After the test, samples of the same batch specifications were taken, placed in a 150°C oven, and taken out after 72 hours. The tensile performance test was performed under the same test conditions to evaluate the high-temperature resistance of the samples. Generally speaking, the smaller the difference, the better the high-temperature resistance, and vice versa. The yellowing index was tested according to the standard GB / T 2409-1980. The samples were accelerated aged for 800 hours in a xenon lamp aging instrument to test the yellowness index of the film and evaluate the sample's anti-ultraviolet aging performance.

[0032] According to the test results, the functional materials prepared with unmodified diatomaceous earth as an additive have obviously reduced their performance to a certain extent, especially the high temperature resistance and UV resistance. The reason for the decline in mechanical properties may be due to the poor compatibility between them.

[0033] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal description of the claims, or if they include equivalent structural elements that are not substantially different from the literal description of the claims, then these other embodiments should also be included in the scope of the claims.

[0034] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A functional material for anti-aging outdoor seats, characterized in that: According to parts by weight, the following raw materials are included: 65-85 parts of polyethylene, 5-15 parts of compatibilizer, 3.5-6.5 parts of diatomaceous earth functional material, 1-5 parts of calcium carbonate whiskers, 0.5-1.5 parts of lubricant, 5-10 parts of toughening agent, 0.1-0.5 parts of antioxidant; The diatomite functional material is prepared by modifying the surface of diatomite with a macromolecular substance having an alternating connection structure of perylene imide and benzophenone.

2. The functional material for anti-aging outdoor seats according to claim 1, characterized in that: The preparation method of the diatomaceous earth functional material is as follows: Step 1: using a halogen-containing silane coupling agent to modify the surface of the pretreated diatomaceous earth to obtain modified diatomaceous earth; Step 2: activating 3,4,9,10-tetracarboxylic diimide with a methanol aqueous solution of potassium hydroxide to form 3,4,9,10-tetracarboxylic diimide potassium salt; Step 3: Using toluene as a medium, using 3,4,9,10-tetracarboxylic diimide potassium salt as a bridging agent, first grafting with modified diatomaceous earth, and then adding a halogenated ultraviolet absorber to carry out chain extension polymerization to obtain diatomaceous earth functional material.

3. The functional material for anti-aging outdoor seats according to claim 2, characterized in that: The halogen-containing silane coupling agent is any one of 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltrimethoxysilane or 3-bromopropyltriethoxysilane.

4. The functional material for anti-aging outdoor seats according to claim 2, characterized in that: The pretreatment method of the diatomaceous earth is: Add diatomaceous earth to nitric acid, disperse evenly, heat to 70-75°C, stir for 4-8 hours, then discharge, wash to neutrality, and vacuum dry.

5. The functional material for anti-aging outdoor seats according to claim 2, characterized in that: The halogenated ultraviolet absorber is prepared by using ultraviolet absorber BP-2 and halogenated isocyanate as raw materials, controlling the molar ratio of the two to be 1:2, and reacting under the catalytic action of a tin catalyst.

6. The functional material for anti-aging outdoor seats according to claim 5, characterized in that: The halogenated isocyanate is chloroethyl isocyanate or 3-chloropropyl isocyanate.

7. The functional material for anti-aging outdoor seats according to claim 5, characterized in that: The tin catalyst is any one of dibutyltin dilaurate, stannous octoate, and dibutyltin diacetate.

8. The functional material for anti-aging outdoor seats according to claim 5, characterized in that: The mass ratio of the 3,4,9,10-tetracarboxylic diimide potassium salt, the modified diatomaceous earth and the halogenated ultraviolet absorber is 3-5:1:2-3.

9. The functional material for anti-aging outdoor seats according to claim 1, characterized in that: The compatibilizer is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene; the lubricant is polyethylene wax, liquid paraffin or montan wax; the toughening agent is methyl methacrylate-butadiene-styrene terpolymer; the antioxidant is any one of antioxidant 1010, antioxidant 1076 or antioxidant 168.

10. A method for preparing the functional material for anti-aging outdoor seats according to claim 1, characterized in that: The following steps are involved: The first step is to add all the raw materials weighed according to their weight into a blender, control the speed to 800-1000r / min, and mechanically stir and mix for 1-2 hours to form a uniform premix; The second step is to feed the premix into a twin-screw extruder, set the temperature of each zone as follows: zone 1 190-200℃, zone 2 200-210℃, zone 3 210-220℃, zone 4 220-230℃, zone 5 210-220℃, and melt-extrude the premix. The obtained masterbatch is pelletized.

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