Outdoor weatherable plastic composite and method of making same

Abstract

The application relates to the technical field of plastic materials, and discloses an outdoor anti-aging plastic composite material and a preparation method thereof. The prepared plastic composite material comprises the following raw materials in parts by weight: 100 parts of an elastomer, 2-5 parts of a stabilizer, 25-35 parts of a plasticizer, 60-100 parts of reinforcing filler and 2-4 parts of modified anti-aging agent; the elastomer is used as a matrix, and various additives are added to improve the anti-aging performance of the plastic composite material; wherein, the addition of the modified anti-aging agent and the reinforcing filler not only improves the anti-aging performance of the matrix, but also avoids the decrease of the anti-aging performance caused by migration and precipitation.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of plastic materials, in particular to an outdoor anti-aging plastic composite material and a preparation method thereof. BACKGROUND

[0002] The plastic composite material is an elastomer prepared by blending plastic and rubber, and the particles obtained by extruding and granulating or crushing and granulating. At present, plastic particles have been widely used in indispensable parts of sports grounds, home appliances, automobiles, mobile phones, PCs, medical devices, and lighting appliances. In a plastic track, plastic particles can be mixed with an adhesive to spread and pave a plastic ground. In artificial turf, the filling of plastic particles increases the elasticity of the turf and can buffer the impact of athletes on the ground. Many particles on the market for tracks are mostly made of ethylene-propylene-diene rubber. In order to reduce costs, a large amount of plasticizer and filler is added. However, the quality of plastic on the market is unstable, and the anti-aging performance is not good. After adding anti-aging agents and other additives, it is easy to separate and migrate, which leads to easy aging of the plastic, cracking, and reduction of service life. Therefore, a plastic with good anti-aging performance has great market prospects. SUMMARY

[0003] In order to solve the above technical problems, the present application provides an outdoor anti-aging plastic composite material and a preparation method thereof.

[0004] The object of the present application can be achieved by the following technical solutions:

[0005] An outdoor anti-aging plastic composite material comprises the following raw materials by weight: 100 parts of an elastomer, 2-5 parts of a stabilizer, 25-35 parts of a plasticizer, 60-100 parts of a reinforcing filler, and 2-4 parts of a modified anti-aging agent.

[0006] The elastomer is a blend of ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer, and chlorinated polyethylene, and the mass of the three is 100 parts.

[0007] Further, the ethylene-propylene-diene rubber is 20-50 parts, the ethylene-vinyl acetate copolymer is 40-70 parts, and the chlorinated polyethylene is 10-40 parts in the elastomer.

[0008] The modified anti-aging agent is prepared by the following steps:

[0009] Step A1, disperse melamine in ethanol, then add dibutyltin dilaurate, and slowly add allyl isothiocyanate under stirring, increase the system temperature to 45-55℃, stir for 3.5-4.5h, and filter to obtain intermediate product 1;

[0010] Step A2, stirring and dispersing intermediate product 1 with sodium hydroxide and ethanol, then adding epichlorohydrin and reacting for 2-3 hours, distilling under reduced pressure, then slowly adding 25wt% sodium hydroxide solution and heating to 60-70°C and reacting for 2-3 hours, filtering, washing and drying to obtain intermediate product 2;

[0011] Step A3, dispersing gamma-aminopropyltriethoxysilane in an ethanol solution (volume ratio of ethanol and deionized water is 9:1), adjusting pH to 8-9, then adding nanocellulose and ultrasonicating for 10-20 minutes, stirring and reacting for 2-3 hours, then adding intermediate product 2 and refluxing at 65-75°C under nitrogen for 24-48 hours, centrifuging, washing and drying to obtain the modified antioxidant;

[0012] Further, the amount ratio of melamine, ethanol, dibutyltin dilaurate and allyl isothiocyanate in step A1 is 0.01-0.03mol:100mL:0.001-0.005g:0.02-0.06mol;

[0013] Further, the amount ratio of sodium hydroxide, ethanol, epichlorohydrin, sodium hydroxide solution and melamine in step A1 in step A2 is 0.04-0.06g:50mL:0.015-0.035mol:10-15mL:0.01-0.03mol;

[0014] Further, the volume ratio of gamma-aminopropyltriethoxysilane, ethanol solution, nanocellulose and intermediate product 2 in step A3 is 0.5-2g:100mL:1-3g:0.2-1g.

[0015] The reinforcing filler is prepared by the following steps: stirring and uniformly dispersing nanometer titanium dioxide in 0.2-2mol / L sodium carbonate solution, then slowly adding 0.5-4mol / L calcium chloride solution and stirring and reacting for 5-10 minutes, filtering, washing, then precipitating in deionized water for 24 hours, filtering and drying to obtain the reinforcing filler;

[0016] Further, the amount ratio of nanometer titanium dioxide, sodium carbonate solution, calcium chloride solution and deionized water in the reinforcing filler is 1-3g:50-100mL:100-200mL:100mL.

[0017] A preparation method of an outdoor anti-aging plastic composite material comprises the following steps:

[0018] Step S1, weighing raw materials according to weight parts, putting the rubber and plastic elastomer into a mixing mill, then sequentially adding stabilizer, reinforcing filler, plasticizer and modified antioxidant, mixing at 100-150°C for 8-12 minutes, discharging, and then sheeting and discharging to obtain a mixed rubber;

[0019] Step S2, transfer the rubber compound to the open mill, refine, sheet, and then extrude in the extruder to obtain a rubber sheet;

[0020] Step S3, irradiate the rubber sheet to crosslink, cut and crush to obtain the plastic composite material.

[0021] The beneficial effects of the present application are:

[0022] The plastic composite material prepared by the present application is based on an elastomer as a matrix, and various additives are added to improve the aging resistance of the plastic composite material. The addition of the modified anti-aging agent and the reinforcing filler not only improves the aging resistance of the matrix, but also avoids the decrease in aging resistance caused by migration and precipitation.

[0023] In the modified anti-aging agent, first, -NH2 in melamine reacts with -N=C=S in allyl isothiocyanate to form intermediate product 1; then, ring-opening reaction occurs between the epoxy group in epichlorohydrin and the amino group in intermediate product 1, and the chloromethyl group and the hydroxyl group in the product react under alkaline conditions to form a new epoxy group, obtaining intermediate product 2; finally, the nanocellulose is modified by using a silane coupling agent, and then intermediate product 2 is grafted onto the nanocellulose to obtain the modified anti-aging agent. The addition of the modified anti-aging agent can significantly improve the anti-aging performance of the matrix. This is because the amino compound and triazine structure contained in the modified anti-aging agent can effectively scavenge free radicals, inhibit the chain reaction of free radicals, delay the aging phenomenon of the matrix in the external environment, and thus improve the service life of the matrix. The carbon-carbon double bond structure contained in the modified anti-aging agent can combine with the molecules of the elastomer during vulcanization, fixing the anti-aging agent molecules on the elastomer molecular chain, greatly limiting the movement of the anti-aging agent molecules, and thus improving the anti-volatilization and anti-migration performance of the anti-aging agent, improving the "blooming" phenomenon of the matrix, reducing the migration in the matrix, and more continuously exerting the anti-aging ability. The anti-aging agent can weaken the interaction between the active groups of the filler, prevent intermolecular attraction and aggregation, thereby promoting the dispersion of the filler and further improving the anti-aging performance. The thiourea structure contained in the anti-aging agent can also be used as a vulcanization accelerator, which can accelerate the vulcanization speed and reduce the energy consumption in the vulcanization process. In addition, the introduction of nanocellulose also improves the mechanical properties of the plastic matrix.

[0024] The addition of the reinforcing filler improves the anti-ultraviolet performance of the matrix, thereby improving the outdoor aging resistance of the matrix. Titanium dioxide can absorb and scatter ultraviolet light entering the film layer, convert light energy into heat energy, and then consume ultraviolet light, thereby avoiding aging caused by ultraviolet light. The coating of calcium carbonate can reduce the production cost of the matrix and improve the mechanical properties of the matrix. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application. Embodiment

[0026] The modified antioxidant is prepared by the following steps:

[0027] Step A1, 0.01 mol of melamine is uniformly dispersed in 100 mL of ethanol, 0.001 g of dibutyltin dilaurate is added, and 0.02 mol of allyl isothiocyanate is slowly added under stirring, the system temperature is raised to 45°C, stirring reaction is carried out for 3.5 h, and then filtration is performed, to obtain intermediate product 1;

[0028] Step A2, 0.04 g of sodium hydroxide and 50 mL of ethanol are added to the intermediate product 1 and stirred and dispersed, 0.015 mol of epichlorohydrin is added for reaction for 2 h, vacuum distillation is performed, 10 mL of 25 wt% sodium hydroxide solution is slowly added dropwise, and the temperature is raised to 60°C for reaction for 2 h, and then filtration, washing and drying are performed, to obtain intermediate product 2;

[0029] Step A3, 0.5 g of γ-aminopropyltriethoxysilane is dispersed in 100 mL of an ethanol solution (the volume ratio of ethanol to deionized water is 9:1), the pH is adjusted to 8, 1 g of nanocellulose is added and ultrasonically treated for 10 min, stirring reaction is carried out for 2 h, 0.2 g of intermediate product 2 is added, and refluxing is carried out at 65°C under nitrogen for 24 h, and then centrifugation, washing and drying are performed, to obtain the modified antioxidant.

[0030] The reinforcing filler is prepared by the following steps:

[0031] 1 g of nanometer titanium dioxide is added to 50 mL of a 0.2 mol / L sodium carbonate solution and stirred uniformly, 100 mL of a 0.5 mol / L calcium chloride solution is slowly added and stirred for reaction for 5 min, filtration, washing, precipitation in 100 mL of deionized water for 24 h, filtration and drying are performed, to obtain the reinforcing filler. Embodiment

[0032] The modified antioxidant is prepared by the following steps:

[0033] Step A1, 0.02 mol of melamine is uniformly dispersed in 100 mL of ethanol, 0.003 g of dibutyltin dilaurate is added, and 0.04 mol of allyl isothiocyanate is slowly added under stirring, the system temperature is raised to 50°C, stirring reaction is carried out for 4 h, and then filtration is performed, to obtain intermediate product 1;

[0034] Step A2, 0.05 g of sodium hydroxide and 50 mL of ethanol were added to the intermediate product 1 and stirred to disperse, then 0.025 mol of epichlorohydrin was added and reacted for 2.5 h, distilled under reduced pressure, then 12 mL of 25 wt% sodium hydroxide solution was slowly added dropwise and the temperature was raised to 65°C and reacted for 2.5 h, filtered, washed, and dried to obtain the intermediate product 2;

[0035] Step A3, 1 g of γ-aminopropyltriethoxysilane was dispersed in 100 mL of ethanol solution (volume ratio of ethanol to deionized water was 9:1), the pH was adjusted to 8.5, then 2 g of nanocellulose was added and ultrasonicated for 15 min, stirred and reacted for 2.5 h, then 0.5 g of intermediate product 2 was added and refluxed at 70°C under nitrogen for 36 h, centrifuged, washed, and dried to obtain the modified antioxidant.

[0036] The reinforcing filler was prepared by the following steps:

[0037] 2 g of nanometer titanium dioxide was added to 80 mL of 1 mol / L sodium carbonate solution and stirred uniformly, then 150 mL of 2 mol / L calcium chloride solution was slowly added and stirred for 8 min, filtered, washed, then precipitated in 100 mL of deionized water for 24 h, filtered, and dried to obtain the reinforcing filler. Example

[0038] The modified antioxidant was prepared by the following steps:

[0039] Step A1, 0.03 mol of melamine was added to 100 mL of ethanol and dispersed uniformly, then 0.005 g of dibutyltin dilaurate was added and the temperature of the system was raised to 55°C, then 0.06 mol of allyl isothiocyanate was slowly added under stirring, and the reaction was stirred for 4.5 h, then filtered to obtain the intermediate product 1;

[0040] Step A2, 0.06 g of sodium hydroxide and 50 mL of ethanol were added to the intermediate product 1 and stirred to disperse, then 0.035 mol of epichlorohydrin was added and reacted for 3 h, distilled under reduced pressure, then 15 mL of 25 wt% sodium hydroxide solution was slowly added dropwise and the temperature was raised to 70°C and reacted for 3 h, filtered, washed, and dried to obtain the intermediate product 2;

[0041] Step A3, 2 g of γ-aminopropyltriethoxysilane was dispersed in 100 mL of ethanol solution (volume ratio of ethanol to deionized water was 9:1), the pH was adjusted to 9, then 3 g of nanocellulose was added and ultrasonicated for 20 min, stirred and reacted for 3 h, then 1 g of intermediate product 2 was added and refluxed at 75°C under nitrogen for 48 h, centrifuged, washed, and dried to obtain the modified antioxidant.

[0042] The reinforcing filler was prepared by the following steps:

[0043] 3g nano-titanium dioxide was added into 100mL 2mol / L sodium carbonate solution and stirred uniformly, then 200mL 4mol / L calcium chloride solution was slowly added and stirred for 10min, filtered, washed, precipitated in 100mL deionized water for 24h, filtered and dried to obtain the reinforced filler. Embodiment

[0044] A preparation method of an outdoor anti-aging plastic composite material comprises the following steps:

[0045] 100 parts of rubber plastic elastomer, 2 parts of stabilizer (calcium-zinc composite stabilizer), 25 parts of plasticizer (paraffin oil), 60 parts of the reinforced filler prepared in Embodiment 1, and 2 parts of the modified antioxidant prepared in Embodiment 1;

[0046] Further, the rubber plastic elastomer is obtained by blending 20 parts of ethylene-propylene-diene rubber, 40 parts of ethylene-vinyl acetate copolymer and 40 parts of chlorinated polyethylene;

[0047] Step S1, the raw materials are weighed, the rubber plastic elastomer is put into the internal mixer, then the stabilizer (calcium-zinc composite stabilizer), the reinforced filler prepared in Embodiment 1, the plasticizer (paraffin oil) and the modified antioxidant prepared in Embodiment 1 are sequentially added, and mixing is carried out at 100℃ for 8min, and the product is discharged and sheeted to obtain a mixed rubber;

[0048] Step S2, the mixed rubber is transferred to an open mill, refined, sheeted, and then extruded in an extruder to obtain a rubber sheet;

[0049] Step S3, the rubber sheet is irradiated and crosslinked, cut and crushed to obtain a plastic composite material. Embodiment

[0050] A preparation method of an outdoor anti-aging plastic composite material comprises the following steps:

[0051] 100 parts of rubber plastic elastomer, 3 parts of stabilizer (calcium-zinc composite stabilizer), 30 parts of plasticizer (paraffin oil), 80 parts of the reinforced filler prepared in Embodiment 2, and 3 parts of the modified antioxidant prepared in Embodiment 2;

[0052] Further, the rubber plastic elastomer is obtained by blending 30 parts of ethylene-propylene-diene rubber, 50 parts of ethylene-vinyl acetate copolymer and 20 parts of chlorinated polyethylene;

[0053] Step S1, the raw materials are weighed, the rubber plastic elastomer is put into the internal mixer, then the stabilizer (calcium-zinc composite stabilizer), the reinforced filler prepared in Embodiment 2, the plasticizer (paraffin oil) and the modified antioxidant prepared in Embodiment 2 are sequentially added, and mixing is carried out at 130℃ for 10min, and the product is discharged and sheeted to obtain a mixed rubber;

[0054] Step S2, transfer the rubber compound to an open mill, refine, sheet, and then extrude in an extruder to obtain a rubber sheet;

[0055] Step S3, irradiate the rubber sheet to crosslink, cut, and crush to obtain the plastic composite material. Example

[0056] A preparation method of an outdoor anti-aging plastic composite material includes the following steps:

[0057] 50 parts of a ternary ethylene-propylene-diene rubber, 40 parts of an ethylene-vinyl acetate copolymer, and 10 parts of chlorinated polyethylene are blended to obtain the rubber plastic elastomer.

[0058] Further, the rubber plastic elastomer is obtained by blending 50 parts of a ternary ethylene-propylene-diene rubber, 40 parts of an ethylene-vinyl acetate copolymer, and 10 parts of chlorinated polyethylene.

[0059] Step S1, weigh the raw materials, and then put the rubber plastic elastomer into a mixing mill, and then sequentially add a stabilizer (a calcium-zinc composite stabilizer), a reinforcing filler prepared in Example 3, a plasticizer (paraffin oil), and a modified antioxidant prepared in Example 3, and mix at 150°C for 12 minutes, and then discharge and sheet to obtain a rubber compound.

[0060] Step S2, transfer the rubber compound to an open mill, refine, sheet, and then extrude in an extruder to obtain a rubber sheet.

[0061] Step S3, irradiate the rubber sheet to crosslink, cut, and crush to obtain the plastic composite material.

[0062] Comparative Example 1

[0063] This comparative example is a plastic composite material, which is different from Example 6 in that titanium dioxide is used instead of the reinforcing filler prepared in Example 3, and the rest are the same.

[0064] Comparative Example 2

[0065] This comparative example is a plastic composite material, which is different from Example 6 in that antioxidant 1010 is used instead of the modified antioxidant prepared in Example 3, and the rest are the same.

[0066] The plastic composite materials prepared in Examples 4-6 and Comparative Examples 1-2 are injection molded into dumbbell-shaped samples at 150°C, and the anti-aging performance is tested.

[0067] Ultraviolet aging performance test: the tensile strength and elongation at break of the sample before aging are tested, then the sample is placed in a xenon aging test chamber for 400h, and the tensile strength and elongation at break are tested again, the chamber radiates ultraviolet light of 290-340nm, the rated power is 1.8kW, the temperature is (60±3)℃, and the relative humidity is (50±5)%;

[0068] Heat aging performance test: the sample is placed in an aging oven at (85±3)℃, and continuously heated under forced ventilation for 5d, and the tensile strength and elongation at break of the sample after heat aging are tested, according to GB / T 528-2009, the tensile strength and elongation at break of the dumbbell-shaped tensile sample are tested by using a universal testing machine;

[0069] The test results are shown in the following table:

[0070]

[0071] As can be seen from the above table, the plastic composite material prepared by the application has excellent aging resistance after the ultraviolet aging performance and heat aging performance tests, and therefore can be widely used outdoors.

[0072] The above content is only an example and description of the concept of the application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace them, as long as they do not deviate from the scope defined by the concept of the application, and they should belong to the protection scope of the application.

Claims

1. An outdoor weatherable plastic composite, characterized in that, The raw materials include the following components by weight: 100 parts of an elastomer, 2-5 parts of a stabilizer, 25-35 parts of a plasticizer, 60-100 parts of a reinforcing filler, and 2-4 parts of a modified antioxidant; The elastomer is obtained by blending ethylene-propylene-diene rubber, ethylene-vinyl acetate copolymer and chlorinated polyethylene, and the total mass of the three is 100 parts; The modified antioxidant is prepared by the following steps: Step A1, melamine is dispersed in ethanol, then dibutyltin dilaurate is added, and allyl isothiocyanate is slowly added under stirring, the system temperature is raised to 45-55℃, and the reaction is stirred for 3.5-4.5h, then the intermediate product 1 is obtained by filtration, the amount ratio of melamine, ethanol, dibutyltin dilaurate and allyl isothiocyanate is 0.01-0.03mol:100mL:0.001-0.005g:0.02-0.06mol; Step A2, sodium hydroxide and ethanol are added to the intermediate product 1 and stirred to disperse, then epichlorohydrin is added and reacted for 2-3h, then it is distilled under reduced pressure, then 25wt% sodium hydroxide solution is slowly added dropwise, and the temperature is raised to 60-70℃ and reacted for 2-3h, then it is filtered, washed and dried to obtain the intermediate product 2; Step A3, γ-aminopropyl triethoxysilane is dispersed in an ethanol solution, the pH is adjusted to 8-9, then nanocellulose is added and ultrasonicated for 10-20min, then it is stirred for 2-3h, then the intermediate product 2 is added, and the system is refluxed at 65-75℃ under nitrogen for 24-48h, then it is centrifuged, washed and dried to obtain the modified antioxidant; The elastomer includes 20-50 parts of ethylene-propylene-diene rubber, 40-70 parts of ethylene-vinyl acetate copolymer and 10-40 parts of chlorinated polyethylene; The reinforcing filler is prepared by the following steps: nanometer titanium dioxide is added to a 0.2-2mol / L sodium carbonate solution and stirred uniformly, then a 0.5-4mol / L calcium chloride solution is slowly added and stirred for 5-10min, then it is filtered, washed, precipitated in deionized water for 24h, filtered and dried to obtain the reinforcing filler.

2. The outdoor weatherable plastic composite material of claim 1, wherein, The amount ratio of sodium hydroxide, ethanol, epichlorohydrin, sodium hydroxide solution in step A2 and melamine in step A1 is 0.04-0.06g:50mL:0.015-0.035mol:10-15mL:0.01-0.03mol.

3. The outdoor weatherable plastic composite material of claim 1, wherein The volume ratio of γ-aminopropyl triethoxysilane, ethanol solution, nanocellulose and intermediate product 2 in step A3 is 0.5-2g:100mL:1-3g:0.2-1g.

4. The outdoor weatherable plastic composite material of claim 1, wherein, The amount ratio of nanometer titanium dioxide, sodium carbonate solution, calcium chloride solution and deionized water in the reinforcing filler is 1-3g:50-100mL:100-200mL:100mL.

5. The preparation method of the outdoor weatherable plastic composite material according to claim 1, characterized in that, The method includes the following steps: Step S1, the raw materials are weighed by weight parts, the elastomer is put into a mixer, then the stabilizer, the reinforcing filler, the plasticizer and the modified antioxidant are added in sequence, and the mixture is mixed at 100-150℃ for 8-12min, then the mixture is discharged and sheeted to obtain the mixed rubber; Step S2, transferring the rubber compound to an open mill, refining, sheeting, and extruding in an extruder to obtain a rubber plate; Step S3, irradiating and cross-linking the rubber plate, cutting and crushing to obtain the plastic composite material.

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