Waste fan blade crushed material modified high polymer material and preparation method thereof

Abstract

The invention discloses a preparation method of a waste fan blade crushed material modified high polymer material, which comprises the following steps: S1, crushing waste fan blades by a crusher, and grinding the crushed material into powder by a crusher, s2, weighing the waste fan blade crushed material, the surface modified resin, the polar resin and the stearic acid lubricant according to a formula ratio; s3, the weighed materials are sequentially put into an internal mixer, the internally mixed materials are added into a single-screw extruder for granulation, and filling modified master batches are obtained; and S4, mixing the filling modified master batch with polymer resin, and granulating by a twin-screw extruder to obtain the modified polymer material. The preparation method provided by the invention solves the problem that the crushed material of the waste fan blade is difficult to add in a plastic product, also improves the mechanical properties and processability of the material, and provides an efficient and environment-friendly solution for recycling and reusing the waste of the fan blade.

Description

Technical Field

[0001] The invention relates to the technical field of composite material recovery and reuse, and in particular to a waste fan blade crushed material modified polymer material and a preparation method thereof. Background Art

[0002] As an important part of the wind power generation system, wind turbine blades have a complex material composition, mainly including reinforcing fibers (such as glass fiber GFRs), thermoplastics (such as polyethylene, polyurethane, polypropylene, polyvinyl chloride) and thermosetting resins (such as epoxy resin, vinyl ester, polyester). Due to the difficulty of remelting thermosetting composite materials, stable chemical properties, and long degradation time, discarded wind turbine blades have become the main recycling difficulty faced by the composite materials industry. Although landfill is the most common and cheapest treatment method, non-degradable materials that remain in the environment for a long time will pollute the soil, air and groundwater, posing a threat to human health. Therefore, due to the cross-linked structure of wind turbine blades and their difficulty in reprocessing or reuse, they have become the main recycling difficulty faced by the composite materials industry, and have increased the pressure to develop sustainable, environmentally friendly and efficient products.

[0003] Currently, there are three difficulties in adding waste blade crushed materials into plastic products: first, the crushed materials contain a variety of components, including epoxy resin, glass fiber, structural adhesive, balsa wood, PVC foam / PET foam, etc. Since the blades are made of epoxy resin infusion molding, it is difficult to separate the components. If they are not separated, the properties of the components are different and they are not compatible with the resin; second, epoxy resin and PVC foam have poor shear resistance and are prone to charring when processed with polymers; third, balsa wood has a porous structure, and direct addition has a greater impact on the melt viscosity. Summary of the invention

[0004] In view of the above problems, the present invention proposes an innovative solution, which satisfies the addition requirements of most polymer materials by reasonably processing the crushed materials, while reducing costs and facilitating promotion.

[0005] In one aspect, the present invention provides a method for preparing a polymer material modified from waste fan blade crushed material, comprising the following steps:

[0006] Step S1: crushing the waste fan blades by a crusher, grinding the crushed materials by a pulverizer, and stirring them in a homogenizing bin to obtain the waste fan blade crushed materials with relatively uniform components;

[0007] Step S2: weighing the waste fan blade crushed material, the surface modified resin, the polar resin and the stearic acid lubricant according to the formula ratio;

[0008] Step S3: putting the weighed materials into an internal mixer in sequence, and adding the internally mixed materials into a single screw extruder for granulation to obtain a filling modified masterbatch;

[0009] Step S4: After mixing the filled modified masterbatch with the polymer resin, granulating the mixture through a twin-screw extruder to obtain a modified polymer material.

[0010] In certain embodiments, the crusher in step S1 is a roller crusher, a hammer crusher or an impact crusher, and the crushing size is 1-3 cm; the pulverizer is a spherical mill; and the size of the powder after grinding is 20-200 mesh.

[0011] In certain embodiments, the stirring speed in step S1 is 30-300 r / min, and the single stirring quantity is 1-5 tons.

[0012] In certain embodiments, the method further comprises, in step S1, sieving the ground material using a 100-mesh, 150-mesh or 200-mesh filter.

[0013] In certain embodiments, the weight fractions of the components in step S2 are:

[0014]

[0015] Among them: the ratio of the surface modified resin and the polar resin can be adjusted according to the composition and properties of the waste fan blade crushed material to achieve the best compatibility and mechanical properties.

[0016] The amount of stearic acid lubricant used can be adjusted according to the lubrication requirements and anti-coking effect during processing.

[0017] In certain embodiments, the surface-modified resin includes one or a mixture of two or more of petroleum resin, rosin resin, and terpene resin;

[0018] The polar resin includes maleic anhydride graft, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EAA), ethylene-methacrylic acid copolymer (EMA for short), and ethylene butyl acrylate (EBA);

[0019] The stearic acid lubricant includes one of stearic acid, stearate, stearic acid ester and stearic acid amide.

[0020] In certain embodiments, the banburying temperature in step S3 is 110-170°C, preferably 150°C; the banburying time is 10-30 minutes, preferably 20 minutes; the extrusion temperature of the single screw extruder is 130-190°C, preferably 180°C; the extruder speed is 60-300r / min, preferably 100r / min.

[0021] In certain embodiments, the polymer resin in step S4 includes one of PE, PP, PBT, PET, PA, PPS, PC, and ABS.

[0022] In certain embodiments, the method further includes cleaning and removing impurities from the waste fan blades before preparing the modified polymer material to remove stains and impurities on the surface of the blades.

[0023] In certain embodiments, the processing temperature of the twin-screw extruder in step S4 is 150-350° C., preferably 200-250° C.; the speed of the extruder is 100-600 r / min, preferably 300-400 r / min.

[0024] On the other hand, the waste fan blade crushed material modified polymer material provided by the present invention is prepared by the following preparation method:

[0025] Step S1: crushing the waste fan blades by a crusher, grinding the crushed materials by a pulverizer, and stirring them in a homogenizing bin to obtain the waste fan blade crushed materials with relatively uniform components;

[0026] Step S2: weighing the waste fan blade crushed material, the surface modified resin, the polar resin and the stearic acid lubricant according to the formula ratio;

[0027] Step S3: putting the weighed materials into an internal mixer in sequence, and adding the internally mixed materials into a single screw extruder for granulation to obtain a filling modified masterbatch;

[0028] Step S4: After mixing the filled modified masterbatch with the polymer resin, granulating the mixture through a twin-screw extruder to obtain a modified polymer material.

[0029] Beneficial effects:

[0030] Improved compatibility: The rich unsaturated bonds and active reaction groups of terpene resin are used to coat the surface of the crushed material, thereby improving the compatibility between the components.

[0031] Pore ​​filling: The lower viscosity of terpene resin can effectively fill pores, avoiding the influence of different material properties on the performance of the filling resin.

[0032] Anti-coking: The use of stearic acid lubricants effectively avoids coking abnormalities caused by high shear heat during processing.

[0033] Reinforcement effect: Due to the presence of glass fiber, it still has a high aspect ratio even after being crushed, and has a significant reinforcement effect on the resin after filling.

[0034] The preparation method of the present invention not only solves the difficulty of adding waste wind turbine blade crushed materials into plastic products, but also improves the mechanical properties and processing properties of the material, and provides an efficient and environmentally friendly solution for the recycling and reuse of wind turbine blade waste. DETAILED DESCRIPTION

[0035] The present invention is further described in detail below through embodiments.

[0036] Example 1

[0037] Step S1: The discarded fan blades are preliminarily crushed using a roller crusher to fragments with a size of 1-2 cm. Subsequently, the fragments are further ground using a ball mill, sieved through a 100-mesh filter, and 2 tons of crushed material is stirred at a speed of 30 r / min through a homogenizing bin to obtain a 100-mesh discarded fan blade crushed material.

[0038] Step S2: weigh the following materials according to the formula: 60 parts of waste fan blade crushed material, 12 parts of petroleum resin, 20 parts of PE-g-MAH, and 8 parts of zinc stearate.

[0039] Step S3: The weighed materials are sequentially put into an internal mixer and internally mixed at a temperature of 150° C. for 20 minutes. After that, the internally mixed materials are added to a single screw extruder and granulated at an extrusion temperature of 180° C. and a rotation speed of 100 r / min to obtain a filled modified masterbatch.

[0040] Step S5: The obtained filled modified masterbatch is mixed with PE resin in a ratio of 1:1, and granulated by a twin-screw extruder at a processing temperature of 200° C. and a rotation speed of 400 r / min to finally obtain a modified polymer material.

[0041] Example 2

[0042] Step S1: Use an impact crusher to crush the waste fan blades into fragments with a size of about 1 cm, then grind them with a ball mill, and stir 5 tons of crushed materials at a speed of 300 r / min through a homogenizing bin to obtain waste fan blade crushed materials with a powder size of 200 mesh.

[0043] Step S2: weigh the following materials according to the formula: 75 parts of waste fan blade crushed material, 5 parts of terpene resin, 10 parts of POE-g-MAH, 5 parts of EBA, and 5 parts of stearic acid amide.

[0044] Step S3: The material was put into an internal mixer and mixed at 170° C. for 10 minutes, and then pelletized by a single screw extruder at 190° C. and 200 r / min.

[0045] Step S5: The filled modified masterbatch and the PBT resin are mixed in a ratio of 1:1, and granulated by a twin-screw extruder at 240° C. and 200 r / min to obtain a modified polymer material.

[0046] Example 3

[0047] Step S1: Use a hammer crusher to crush the waste fan blades into fragments with a size of 2-3 cm, then use a ball mill to grind the fragments, and sieve them through a 150-mesh filter. The homogenizing bin stirs 3 tons of crushed material at a speed of 150 r / min to obtain a powder of waste fan blade crushed material with a powder size of 150 mesh.

[0048] Step S2: weigh the following materials according to the formula: 70 parts of waste fan blade crushed material, 8 parts of a mixture of rosin resin and terpene resin (50% each), 20 parts of EVA, and 2 parts of calcium stearate.

[0049] Step S3: The material is put into an internal mixer and mixed at 150° C. for 15 minutes. Then, the material is pelletized by a single screw extruder at 160° C. and 150 r / min.

[0050] Step S5: The filled modified masterbatch and the PP resin are mixed in a ratio of 2:1, and granulated by a twin-screw extruder at 250° C. and 300 r / min to obtain a modified polymer material.

[0051] Comparative Example 1

[0052] Similar to Example 1, but without using zinc stearate as lubricant.

[0053] Comparative Example 2

[0054] Similar to Example 2, but directly using unmodified waste fan blade crushed material (without the treatment of steps S2 and S3), its compatibility with PBT resin was observed.

[0055] Comparative Example 3

[0056] Similar to Example 3, but using conventional calcium carbonate resin as filler and not using waste fan blade crushed material, the mechanical properties and reinforcement effect were observed.

[0057] The performance tests of Examples 1-3 and Comparative Examples 1-3 were carried out, and the test results are shown in the following table:

[0058]

[0059] Results Analysis

[0060] The modified polymer materials obtained in Examples 1-3 all exhibited good compatibility and mechanical properties, especially in terms of anti-coking, pore filling and reinforcement.

[0061] Since zinc stearate was not used as a lubricant in Comparative Example 1, obvious coking occurred during the processing, which affected the quality of the material.

[0062] In Comparative Example 2, unmodified waste fan blade crushed material is directly used, and its processing performance is poor, so the material cannot be formed.

[0063] Comparative Example 3 uses conventional fillers. Although the material itself has stable performance, it lacks the reinforcing effect of the waste fan blade crushed material and has relatively low mechanical properties.

[0064] In summary, the preparation method of the present invention successfully solves the difficulty of adding waste wind turbine blade crushed materials into plastic products through reasonable processing and formula design, improves the mechanical properties and processing properties of the material, and provides an efficient and environmentally friendly solution for the recycling and reuse of wind turbine blade waste.

[0065] The above description is only a preferred embodiment of the present invention. It should be pointed out that, for ordinary technicians in this field, several modifications and improvements can be made without departing from the creative concept of the present invention, and these should also be regarded as within the scope of protection of the invention.

Claims

1. A method for preparing a polymer material modified from waste fan blade crushed material, characterized in that: The following steps are involved: Step S1: crushing the waste fan blades by a crusher, grinding the crushed materials by a pulverizer, and stirring them in a homogenizing bin to obtain the waste fan blade crushed materials with relatively uniform components; Step S2: weighing the waste fan blade crushed material, the surface modified resin, the polar resin and the stearic acid lubricant according to the formula ratio; Step S3: putting the weighed materials into an internal mixer in sequence, and adding the internally mixed materials into a single screw extruder for granulation to obtain a filling modified masterbatch; Step S4: After mixing the filled modified masterbatch with the polymer resin, granulating the mixture through a twin-screw extruder to obtain a modified polymer material.

2. The method for preparing a polymer material modified from waste fan blade crushed material according to claim 1, characterized in that: In step S1, the crusher is a roller crusher, a hammer crusher or an impact crusher, and the crushing size is 1-3 cm; the pulverizer is a spherical mill; and the size of the powder after grinding is 20-200 meshes.

3. The method for preparing a polymer material modified from waste fan blade crushed material according to claim 1, characterized in that: In step S1, the stirring speed is 30-300 r / min, and the single stirring quantity is 1-5 tons.

4. The method for preparing a polymer material modified from waste fan blade crushed material according to claim 1, characterized in that: The weight proportions of each component in step S2 are:

5. The method for preparing a polymer material modified from waste fan blade crushed material according to claim 4, characterized in that: The surface modified resin includes one or a mixture of two or more of petroleum resin, rosin resin, and terpene resin; The polar resin includes maleic anhydride grafts, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid copolymers, and ethylene butyl acrylate; the maleic anhydride grafts include PE-g-MAH, POE-g-MAH, or SBS-g-MAH; The stearic acid lubricant includes one of stearic acid, stearate, stearic acid ester and stearic acid amide.

6. The method for preparing a polymer material modified from waste fan blade crushed material according to claim 1, characterized in that: In step S3, the banburying temperature is 110-170°C, preferably 150°C; the banburying time is 10-30 minutes, preferably 20 minutes; the extrusion temperature of the single screw extruder is 130-190°C, preferably 180°C; the extruder speed is 60-300r / min, preferably 100r / min.

7. The method for preparing a polymer material modified from waste fan blade crushed material according to claim 1, characterized in that: In step S4, the polymer resin includes one of PE, PP, PBT, PET, PA, PPS, PC, and ABS.

8. The method for preparing a polymer material modified from waste fan blade crushed material according to claim 1, characterized in that: The processing temperature of the twin-screw extruder in step S4 is 150-350° C., preferably 200-250° C.; the speed of the extruder is 100-600 r / min, preferably 300-400 r / min.

9. A polymer material modified from waste fan blade crushed material obtained by the preparation method according to any one of claims 1 to 8.

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