1. The ABS shell powder biomass composite material is characterized by being prepared by extruding the following raw materials, by weight, 50-70 parts of ABS, 20-40 parts of caprolactam modified shell powder, 1-3 parts of polyethylene wax, 1-4 parts of titanium dioxide and 1-3 parts of EVA through double screws.

2. The ABS shell powder biomass composite material as claimed in claim 1, wherein the caprolactam modified shell powder is: adding the shell powder into an ethanol solution of caprolactam, high-mixing at normal temperature, then removing ethanol by high-mixing at 100 +/-10 ℃, and drying to obtain the caprolactam modified shell powder.

3. The ABS shell powder biomass composite material as claimed in claim 2, wherein the mass concentration of the ethanol solution of caprolactam is 10-30%.

4. The ABS shell powder biomass composite material as claimed in claim 2, wherein the preparation method of the shell powder comprises the following steps: removing impurities from shell, cleaning, oven drying, pulverizing, and sieving with 100 mesh sieve.

5. The ABS shell powder biomass composite material as claimed in claim 2, wherein the high-speed mixer for high mixing has a rotation speed of 1000-.

6. The preparation method of the ABS shell powder biomass composite material as claimed in any one of claims 1 to 5, characterized in that the ABS, caprolactam modified shell powder, polyethylene wax, titanium dioxide and EVA are added into a high-speed mixer, mixed uniformly, added into a double-screw extruder for extrusion, granulated and dried to obtain the ABS biomass composite material.

7. The method as claimed in claim 6, wherein the temperatures of the first temperature section to the eighth temperature section of the twin-screw extruder head are set from the feeding section to the extruder head at 190-.

Background

The acrylonitrile-butadiene-styrene copolymer is a terpolymer consisting of acrylonitrile, butadiene and styrene, and is called acrylic-butadiene-styrene copolymer for short. ABS resin has impact resistance, heat resistance, low temperature resistance, chemical resistance and excellent electrical performance, has the advantages of easy processing, stable product dimension, good surface gloss and the like, is easy to coat and color, can be subjected to secondary processing such as surface metal spraying, electroplating, welding, hot pressing, bonding and the like, can be subjected to injection molding, extrusion molding, blow molding, calendering, laminating, foaming and thermoforming by using plastic molding equipment such as an injection molding machine, an extrusion machine and the like, is widely applied to the industrial fields of machinery, automobiles, electronic appliances, instruments and meters, textile, building and the like, and is thermoplastic engineering plastic with extremely wide application.

However, ABS has the disadvantages of low heat distortion temperature, poor weather resistance, high carbon emission and the like, so that the wider application of ABS is limited, and ABS composite materials meeting the actual requirements can be prepared by necessary modification. Chinese patent 201510204768.5 discloses an ABS/shell powder composite material, which is prepared by compounding ABS resin, shell powder, coconut shell fiber, sodium stearyl lactate, maleic anhydride, castor oil, dibenzoyl peroxide, styrene, an aluminate coupling agent, an antioxidant and hydrogenated lanolin, wherein the preparation method of the shell powder comprises the following steps: the shell powder is calcined for l-2h at the temperature of 800-900 ℃, because the main component of the shell powder is calcium carbonate, the shell powder is decomposed into calcium oxide after being calcined at the temperature of 800-900 ℃, the property of the biomass of the shell powder is lost, and the carbon emission is not reduced.

The shell is a natural organic-inorganic hybrid material, and 95% of the main components of the shell are calcium carbonate and a small amount of amino acid and polysaccharide substances. The shell powder is applied to the organic medium ABS, and has two problems: (1) the shell powder particles have great chemical activity and are easy to agglomerate, so that the using effect of the shell powder particles is influenced; (2) the surface is strong polarity, the dispersion is uneven in the high polymer, and the affinity with the high polymer is poor, so that the material performance is reduced due to the defect of the interface of the two materials. Therefore, in order to fully utilize the shell powder, improve the reinforcing effect, and improve the wettability, dispersibility and affinity with organisms in the high polymer, the nano calcium carbonate needs to be subjected to surface modification.

In view of the problems, the invention applies the bio-based material modified shell powder to the selection of the filler, so that the composite material has good mechanical property, the thermal deformation temperature is improved, the carbon emission can be reduced, and the advantages of accelerated biodegradation and low cost are achieved.

Disclosure of Invention

Aiming at the problems, the invention provides an ABS shell powder biomass composite material and a preparation method thereof. According to the invention, a biomass material caprolactam is adopted to modify shell powder, polyethylene wax, titanium dioxide and EVA are added, and are uniformly mixed with ABS, and then the mixture is extruded by a double-screw extruder, granulated and dried to obtain the ABS composite material. The invention solves the problem of poor surface compatibility of the plastic base material and the bio-based filler, and has the advantages of good mechanical property of the composite material, improved thermal deformation temperature, reduced carbon emission, accelerated biodegradation and low cost.

The invention aims to provide an ABS shell powder biomass composite material which is characterized by being prepared by extruding the following raw materials, by weight, 50-70 parts of ABS, 20-40 parts of caprolactam modified shell powder, 1-3 parts of polyethylene wax, 1-4 parts of titanium dioxide and 1-3 parts of EVA (ethylene-vinyl acetate copolymer).

The caprolactam modified shell powder is prepared by the following method: adding the shell powder into an ethanol solution (with the mass concentration of 10-30%) of caprolactam for cold mixing (high mixing at normal temperature), then removing the ethanol by high mixing at 100 +/-10 ℃, and drying to obtain the caprolactam modified shell powder. Preferably, the rotating speed of the high-speed mixer is 1000-. Preferably, the shell powder is prepared by: removing impurities from shell, cleaning, oven drying, pulverizing, and sieving with 100 mesh sieve.

The invention also aims to provide a preparation method of the ABS shell powder biomass composite material, which is characterized in that ABS, caprolactam modified shell powder, polyethylene wax, titanium dioxide and EVA are added into a high-speed mixer, are uniformly mixed and then are added into a double-screw extruder for extrusion, granulation and drying, and the ABS biomass composite material is obtained. The temperatures from the first temperature section to the eighth temperature section of the double-screw extruder head are respectively set to be 190-.

According to the invention, the shell powder is modified by adopting a caprolactam surface modifier, the amino group of caprolactam is combined with the hydroxyl group on the surface of calcium carbonate of the shell powder, and the caprolactam is directionally adsorbed on the surface of the shell powder to form a stable adsorption layer, so that the dispersibility, wettability, lipophilicity and stability of the caprolactam are improved; on the other hand, the affinity of the ABS shell powder composite material can be improved, one end of the composite material is surface-linked by caprolactam and shell powder, the other end of the composite material is twisted or crosslinked with a high polymer ABS molecular chain to improve the interface compatibility of the composite material, the interface strength is increased, and the performance of the ABS shell powder composite material is enhanced. As the interface strength is increased, the matrix in the area around the shell powder particles is locally forced to deform in a high-elasticity manner, when the ABS macromolecular chain segment slides, the ABS matrix can be subjected to yielding by larger tensile stress, and the chain segment slides more due to the high tensile stress, so that the tensile deformation is increased. The interface strength is increased, the stress transfer and dispersion effects are enhanced, and meanwhile, the limiting effect of the shell powder on the sliding capacity of the ABS molecular chain is enhanced, so that the bending strength and the bending modulus of the modified composite material are further increased. The modified shell powder filled ABS composite material reduces the molecular chain fracture and cracks of a polymer matrix, so that the impact strength of the ABS composite material is improved. The shell powder with high heat resistance can prevent the heat conduction effect and reduce the rise of the internal thermal decomposition temperature of the composite material to a certain extent. The high-dispersity modified shell powder particles in the composite material can better obstruct the diffusion and heat conduction of heat flow; meanwhile, the strong interface layer of the composite material can be effectively destroyed only by adding caprolactam at a higher decomposition temperature, so that the heat stability of the composite material is improved by modifying the shell powder with caprolactam.

According to the invention, caprolactam modified shell powder, polyethylene wax, titanium dioxide and EVA are added to modify ABS, the shell powder is modified by caprolactam to improve the surface compatibility of a plastic base material and the surface of a bio-based filler, and the mechanical property and the thermal stability of the material, the titanium dioxide is used as a nucleating agent, the polyethylene wax and the EVA (ethylene-vinyl acetate copolymer) improve the lubricating property of the product, and the composite material with the advantages of good surface compatibility of the plastic base material and the bio-based filler, excellent mechanical property, good thermal stability, reduction of carbon emission, acceleration of biodegradation and low cost is obtained by all raw materials in a double screw extruder.

Compared with the prior art, the invention has the following beneficial effects:

1. according to the invention, ABS and the modified shell powder biomass material are blended, the compatibility of the plastic substrate and the surface of the filler is excellent, and the ABS shell powder biomass composite material with excellent mechanical property and high temperature resistance is prepared. On the basis, under the condition of ensuring the mechanical property and the heat resistance of the material, the filling amount of the biomass is increased to the maximum extent, the degradation efficiency of the material is improved, and the material cost is reduced.

2. The ABS biomass composite material can be used for preparing various electrical accessories, electronic accessories, automobile accessories, sound accessories, containers, workpieces and the like by the existing molding methods such as injection, extrusion and the like, and has wide application range.

3. The ABS biomass composite material can be decomposed and absorbed by microorganisms in soil, reduces carbon emission, has little pollution to the environment, and has good environmental benefit and social value.

Detailed Description

The present invention will be further described with reference to the following examples. The ABS used in the examples was Toray 700-X01.

The method for obtaining shell powder used in this example is as follows: removing impurities from shell, cleaning with water, oven drying at 100 deg.C, pulverizing, and sieving to obtain 100 mesh shell powder.

Example 1: preparing modified shell powder:

adding 20g of caprolactam into 80g of absolute ethyl alcohol for mixing to prepare a mixed solution with the mass concentration of 20%, mixing 1000 g of shell powder with the mixed solution, carrying out cold mixing for 30min, then carrying out high mixing at 100 ℃ for 30min to remove the ethyl alcohol, and drying to obtain about 1020 g of caprolactam modified shell powder. The rotating speed of the high-speed mixer is 1000 r/min.

Example 2: preparing modified shell powder:

adding 30g of caprolactam into 70g of absolute ethyl alcohol, mixing to prepare a mixed solution with the mass concentration of 30 wt%, mixing 1000 g of shell powder with the mixed solution, cold mixing for 30min, then high mixing at 100 ℃ for 30min to remove the ethyl alcohol, and drying to obtain about 1030 g of caprolactam modified shell. The rotating speed of the high-speed mixer is 1300 r/min.

Example 3: preparing modified shell powder:

mixing 10 g of caprolactam with 90g of absolute ethyl alcohol to prepare a mixed solution with the mass concentration of 10%, mixing 1000 g of shell powder with the mixed solution, cold mixing for 30min, then high mixing at 100 ℃ for 30min to remove the ethyl alcohol, and drying to obtain about 1010 g of caprolactam modified shell powder. The rotating speed of the high-speed mixer is 1300 r/min.

Example 4: preparation of ABS shell powder composite material

500 g of ABS and 200 g of caprolactam modified shell powder obtained in example 1, 10 g of polyethylene wax, 10 g of titanium dioxide and 10 g of EVA are added into a high-speed stirrer, the materials are uniformly mixed and then added into a double-screw extruder from a side feeding hopper, and the mixed materials are extruded by the double-screw extruder, granulated and dried to obtain the ABS shell powder biomass composite material. The temperatures of the twin-screw extruder from the feed zone to the first temperature zone to the eighth temperature zone of the head were set to 190 ℃, 200 ℃, 200 ℃, 200 ℃, 220 ℃, 200 ℃, 200 ℃, 190 ℃ and the temperature of the die head was 210 ℃.

Example 5: preparation of ABS shell powder composite material

600 g of ABS and 300 g of caprolactam modified shell powder obtained in example 2, 20g of polyethylene wax, 20g of titanium dioxide and 20g of EVA are added into a high-speed stirrer, the materials are uniformly mixed and then added into a double-screw extruder from a side feeding hopper, and the mixed materials are extruded by the double-screw extruder, granulated and dried to obtain the ABS shell powder biomass composite material. The temperatures of the twin-screw extruder from the feed zone to the first temperature zone to the eighth temperature zone of the head were set at 195 ℃, 195 ℃, 190 ℃, 185 ℃, 180 ℃, 180 ℃, 180 ℃ and 195 ℃ respectively, and the temperature of the die head was set at 195 ℃.

Example 6: preparation of ABS shell powder composite material

Adding 700 g of ABS and 400 g of caprolactam modified shell powder obtained in example 3, 30g of polyethylene wax, 30g of titanium dioxide and 30g of EVA into a high-speed stirrer, uniformly mixing, adding into a double-screw extruder from a side feeding hopper, extruding the mixed raw materials through the double-screw extruder, and granulating and drying to obtain the ABS shell powder biomass composite material. The temperatures of the twin-screw extruder from the feed zone to the first temperature zone to the eighth temperature zone of the head were set to 200 ℃, 210 ℃, 210 ℃, 210 ℃, 220 ℃, 200 ℃, 200 ℃, and 200 ℃ respectively, and the temperature of the die head was set to 200 ℃.

Example 7: preparation of ABS shell powder composite material

650 g of ABS and 350 g of caprolactam modified shell powder obtained in example 1, 20g of polyethylene wax, 40 g of titanium dioxide and 20g of EVA are added into a high-speed stirrer, the materials are uniformly mixed and then added into a double-screw extruder from a side feeding hopper, and the mixed materials are extruded by the double-screw extruder, granulated and dried to obtain the ABS shell powder biomass composite material. The temperatures of the twin-screw extruder from the feed zone to the first temperature zone to the eighth temperature zone of the head were set to 200 ℃, 220 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃, 210 ℃ and 220 ℃ for the die head, respectively.

Example 8: preparation of ABS shell powder composite material

550 g of ABS, 350 g of caprolactam modified shell powder obtained in example 2, 20g of polyethylene wax, 30g of titanium dioxide and 10 g of EVA are added into a high-speed stirrer, the materials are uniformly mixed and then added into a double-screw extruder from a side feeding hopper, and the mixed materials are extruded by the double-screw extruder, granulated and dried to obtain the ABS shell powder biomass composite material. The temperatures of the twin-screw extruder from the feed zone to the first temperature zone to the eighth temperature zone of the head were set to 195 ℃, 200 ℃, 200 ℃, 200 ℃, 190 ℃, 190 ℃, 190 ℃ and 200 ℃ respectively, and the temperature of the die head was set to 200 ℃.

The ABS shell powder biomass composites prepared in examples 4 to 8 were processed by injection molding to test bars, which were according to the GBT1040.1-2018 standard. And the mechanical property and the heat distortion temperature are tested, wherein the tensile strength, the elongation at break, the bending strength and the bending modulus are tested according to the measurement of the tensile property of the GB _ T1040.1-2018 plastic. Unnotched impact Strength (KJ/m)²) The test is carried out according to the measurement standard of the GBT1843-2008 plastic cantilever beam impact strength. Heat distortion temperature is a measure of the deformation temperature under load of GBT1634.2-2004 for plastics, hard rubber and long fiber reinforced composites in part 2. The test results are shown in table 1 below.

Table 1: product performance of ABS shell powder composite prepared in examples 4 to 8 processed by injection molding into test specimens

As can be seen from table 1: compared with ABS, the invention adds the biomass material caprolactam modified shell powder, polyethylene wax, titanium dioxide and EVA to modify ABS to obtain the ABS composite material, and the performance indexes of the composite material, such as strength (tensile strength, bending strength and non-notch impact strength), toughness (elongation at break, bending modulus), high temperature resistance (thermal deformation temperature) and the like, are obviously improved.

The embodiment of the present invention is not limited by the above-mentioned embodiments, and various modifications or changes that can be made by those skilled in the art without creative efforts based on the technical solution of the present invention are still within the protection scope of the present invention.