CN111592707B - Plastic product filled and modified by artificial granite waste residue and processing method thereof - Google Patents
Plastic product filled and modified by artificial granite waste residue and processing method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract
The invention discloses a plastic product filled and modified by using artificial granite waste residues and a processing method thereof, wherein the plastic product comprises the following components in parts by mass: 100 portions of resin, 15 to 500 portions of artificial granite waste residue, 0.2 to 15 portions of surface modifier, 0.1 to 5 portions of chain extender, 0.2 to 4 portions of compatibilizer and 0.3 to 2 portions of lubricant. The modified plastic product and the processing method thereof have the advantages of simple process and good economy, are suitable for large-scale production, can reduce the pollution of solid wastes to the environment, realize the resource recycling of the wastes, and can create more benefits for enterprises.
Description
Technical Field
The invention relates to the technical field of recycling of construction wastes, in particular to a plastic product filled and modified by artificial granite waste residues and a processing method thereof.
Background
In the plastic molding process, a certain amount of inorganic powder can be added as a filler to reduce the production cost, and the commonly used filler comprises calcium carbonate, talcum powder, kaolin, wollastonite, barium sulfate, various cheap industrial solid wastes and the like. Among them, calcium carbonate is the most widely used inorganic filler, and has become one of the main additives in the plastic processing industry and plastic products due to its wide source of raw materials, low cost, high whiteness, non-toxicity, and no odor. In recent years, by combining a cross-scale compounding technology of a multi-component material with more advanced processing modes such as banburying kneading and twin-screw extrusion, calcium carbonate is changed from a filler in the traditional sense to a high-performance modifier or a functional assistant, and the filling of a large amount of calcium carbonate can not only effectively reduce the production cost, but also make up for deficiencies, eliminate the weakness of the performance of resin components, and obtain a composite material with excellent comprehensive performances such as mechanical property, heat resistance, aging resistance, dimensional stability and the like.
The calcium carbonate powder for plastics is heavy calcium carbonate with 400-800 meshes in maximum use amount, and the influence of performance indexes such as granularity, distribution, particle shape, oil absorption value, whiteness, purity, moisture content and volatile matter content of the calcium carbonate on plastic products is very important. In addition, the surface of calcium carbonate is hydrophilic and oleophobic, so that the surface energy is high, and agglomerates are easily formed, so that the calcium carbonate is unevenly dispersed in a polymer matrix, and further the properties of elastic modulus, mechanical property, impact strength and the like of a plastic product are influenced, and numerous white spots and hard spots are formed on the product, so that the using effect is influenced. The existing calcium carbonate surface modification method is mainly to directly modify the calcium carbonate by a surfactant and a coupling agent so as to convert the calcium carbonate from inorganic to organic, thereby increasing the compatibility of the calcium carbonate and organic resin. However, the application range of the current surface modifier is limited to calcium carbonate powder with a purity of more than 95%, and the effect of the surface modifier is seriously reduced for calcium carbonate powder containing impurities such as polymer resin and volatile organic compounds.
The artificial granite is prepared by using refined powder of calcium carbonate ores such as calcite, marble, limestone and the like and unsaturated polyester resin as raw materials and through the steps of mixing, stirring, press forming, heating and curing, cutting, polishing and the like. The unsaturated polyester resin is formed by crosslinking unsaturated polyester molecules (long-chain molecules before curing, the molecular weight of the unsaturated polyester molecules is generally 200-3000, and the unsaturated polyester resin mainly comprises propylene glycol, diethylene glycol, phthalic anhydride, maleic anhydride and other components) with styrene monomers under the action of an initiator and an accelerator to form thermosetting reticular macromolecules. The waste artificial granite dregs are produced through precipitation and plate-frame press filtering of a great deal of waste slurry produced in the cutting and polishing processes. The solid content of the artificial granite waste residue after filter pressing is about 80 percent, and the solid content comprises 90 to 92 mass portions of calcium carbonate, 7 to 9 mass portions of thermosetting unsaturated resin and a small amount of volatile impurities. In view of the complex structure of the artificial granite waste residue, a low-cost and large-batch resource utilization method is still lacking at present. Nowadays, enterprises generally adopt simple landfill and open-air stacking, a large amount of volatile organic compounds and powder are generated and are raised along with wind, secondary pollution is caused to the environment, the secondary pollution is a key factor which troubles the sustainable development of the enterprises, and meanwhile, resources are greatly wasted.
Published master academic thesis "He Jiajie application of artificial stone polishing waste powder in HDPE research [ D ]. Guangzhou: 2012 ", south China university of science, discloses a composite material prepared by dissolving surface modifiers such as titanate coupling agent, silane coupling agent, stearic acid and the like with a certain amount of solvent, dripping the dissolved surface modifiers into waste calcium carbonate artificial stone polishing powder, stirring the waste modified polishing powder, premixing the waste modified polishing powder with high-density polyethylene, and performing extrusion molding. The result shows that the polishing waste powder does not have the expected modification effect because unsaturated polyester on the surface of the powder adsorbs a large amount of modifier, but causes the reduction of the tensile strength and the bending strength of a composite system; when the filler is unmodified calcium carbonate artificial stone polishing waste powder, the tensile strength trend is relatively stable, and the descending amplitude is relatively small, so that the calcium carbonate artificial stone polishing waste powder can be added into HDPE without being modified by a surface modifier. The method needs to dissolve the surface modifier in advance, and the surface modifier is not easy to control in the process of dripping into the powder, so that the method is not suitable for industrial stable production. Moreover, when the mass fraction of the calcium carbonate artificial stone polishing waste powder in the composite system is more than 30%, the HDPE composite material prepared by the method can cause the tensile strength and the flexural modulus of the material to be rapidly reduced, so that the method is not suitable for the field of plastic products with high filling amount.
Chinese patent CN 201910343506.5 discloses a composite material of artificial granite waste residue filled polymer and a preparation method thereof, wherein the artificial granite waste residue is directly used as a filler to be compositely modified with one of polyvinyl alcohol, polyurethane, polyamide, polyimide and polyurea after being simply dried and crushed. Although the method is simple and has strong operability, no suggestion is given on whether the five general-purpose plastics of polyethylene, polypropylene, polyvinyl chloride, polystyrene and ABS have the same applicability or not, and no interface characteristics of the artificial granite waste residue and the matrix resin are given, so that how to further improve the compatibility between the artificial granite waste residue and the matrix resin is further provided, and further, a polymer composite material with better comprehensive performance is obtained for further deep research.
Chinese patent CN 201910592897.4 provides a plastic product based on artificial marble waste residue filler and a preparation method thereof, the method comprises the steps of carrying out surface modification treatment on the artificial marble waste residue through aluminate, borate, titanate, phosphate, high-density polyethylene grafted maleic anhydride, polyethylene wax, ethylene-acrylic acid copolymer wax, pentaerythritol stearate, ethylene bis stearamide, a silane coupling agent, a lignin coupling agent, a tin coupling agent or a rare earth coupling agent, and then blending with resin to obtain the plastic product with excellent comprehensive performance. However, the method does not fully consider the characteristics that the resin in the artificial marble waste residue fully wraps the surfaces of the calcium carbonate particles and the organic modification groups on the surfaces of the calcium carbonate particles are greatly reduced, and the mechanical property of the obtained product is poor only by adopting a single surface modifier to activate the calcium carbonate. Therefore, the plastic and the preparation method thereof are needed to change waste artificial granite slag into valuable, simplify the process method, reduce the production cost and improve the performance of the obtained product.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Aiming at the technical problems, the invention provides a plastic product filled and modified by artificial granite waste residues and a processing method thereof, and aims to obtain the plastic product which has simple process, good economy, suitability for large-scale production and obvious economic and social benefits and the processing method thereof.
In order to realize the purpose, the technical scheme provided by the invention is as follows:
a plastic product filled and modified by using artificial granite waste residues comprises the following components in parts by mass: 100 portions of resin, 15 to 500 portions of artificial granite waste residue, 0.2 to 15 portions of surface modifier, 0.1 to 5 portions of chain extender, 0.2 to 4 portions of compatibilizer and 0.3 to 2 portions of lubricant.
Further, the resin is at least one of polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene terpolymer or polylactic acid.
Further, the artificial granite waste residue is obtained according to the following operation steps:
(a) Drying the original artificial granite waste residue at 60-135 ℃ to obtain crude dried waste residue with the water content of 5-8 parts by weight;
(b) Crushing the coarse dry waste residue into refined powder, and controlling the particle size of the powder to be 300-1200 meshes by using grading equipment;
(c) Further drying the crushed and graded powder, and controlling the water content to be less than 0.7 weight part to obtain the nano-composite material;
the artificial granite waste residue obtained after the operation comprises 90 to 92 mass parts of calcium carbonate, 7 to 9 mass parts of thermosetting resin, 0.1 to 0.5 mass part of pigment and 0.3 to 2 mass parts of volatile micromolecular impurities; wherein, the thermosetting resin refers to thermosetting reticular macromolecules formed by crosslinking unsaturated polyester molecules and styrene; the volatile small molecular impurities are styrene, propylene glycol, diethylene glycol, phthalic anhydride and maleic anhydride.
Further, the surface modifier is at least one of stearic acid-aluminate, stearic acid-titanate or stearic acid-borate composite surface modifier; wherein the stearic acid-X acid ester composite surface modifier is prepared by mixing stearic acid and X acid ester at a high speed, the weight ratio of stearic acid in the composite surface modifier is more than 50%, and X represents aluminum, titanium or boron.
Further, the surface modifier is a stearic acid-aluminate composite surface modifier.
Further, the chain extender is a JONCRYL ADR series product produced by BASF company, and JONCRYL ADR 4370-S is preferred.
Further, the compatibilizer is at least one of ethylene-methyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene propylene diene monomer, ethylene-octene copolymer, styrene-ethylene-butene-styrene block copolymer, maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA), maleic anhydride grafted ethylene-octene copolymer (MAH-g-POE), maleic anhydride grafted ethylene propylene diene monomer (MAH-g-EPDM), and maleic anhydride grafted styrene-ethylene-butene-styrene block copolymer (MAH-g-SEBS).
Further, the compatibilizer is maleic anhydride grafted ethylene propylene diene monomer (MAH-g-EPDM).
Further, the lubricant is at least one of stearic acid amide, ethylene bis-stearic acid amide, paraffin, polyethylene wax or low molecular weight polypropylene.
The processing method for filling the modified plastic product by using the artificial granite waste residue comprises the following operation steps:
(1) Weighing the following components in parts by mass: 100 parts of resin, 15-500 parts of artificial granite waste residue, 0.2-15 parts of surface modifier, 0.1-5 parts of chain extender, 0.2-4 parts of compatibilizer and 0.3-2 parts of lubricant;
(2) Mixing the artificial granite waste residue, a surface modifier, a chain extender and a lubricant, and carrying out continuous modification treatment at 50-110 ℃ by a powder surface modifier to obtain modified powder;
(3) And (3) mixing the modified powder, the resin and the compatibilizer at a high speed, adding the mixture into a screw extruder, setting corresponding temperature and rotating speed, extruding and granulating, and then preparing the plastic product through an injection molding machine and a film blowing machine.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method combines the characteristic that the surfaces of calcium carbonate particles in the artificial granite waste residue are fully wrapped by thermosetting resin, utilizes the compatibilizer to effectively improve the interface bonding force between the artificial granite waste residue and matrix resin, and the obtained composite modified plastic product still has excellent comprehensive properties such as tensile strength, elongation at break, impact strength and the like under the condition of high filling proportion that the filling amount of the artificial granite waste residue is more than 40 parts by weight;
(2) According to the invention, a small amount of unreacted components and part of incompletely reacted active groups remained in the artificial granite waste residue are linked with the matrix resin into a whole by adding the reactive resin chain extender, so that the tensile strength and the impact strength of the obtained plastic product are improved to a certain extent compared with the matrix resin;
(3) The invention adopts stearic acid-aluminate, stearic acid-titanate, stearic acid-borate series composite surface modifier which takes stearic acid as main body to modify the surface of the artificial granite waste residue, and the modification effect is better than that of single modifier of aluminate, titanate, borate and stearic acid;
(4) The method has simple process and good economy, is suitable for large-scale production, can reduce the pollution of solid waste to the environment, realizes the resource recycling of the waste, and can create more benefits for enterprises.
Drawings
FIG. 1 is a SEM image of a cross section of a plastic article prepared in example 1 of the present invention.
FIG. 2 is a SEM image of a cross-section of a plastic article prepared in comparative example 1 (comparative example).
Detailed Description
The following detailed description is to be read in connection with the accompanying drawings, but it is to be understood that the scope of the invention is not limited to the specific embodiments. The raw materials used in the examples were all commercially available unless otherwise specified. The artificial granite waste residue is obtained from the market, and the chain extender is a JONCRYL ADR series product produced by BASF company.
Example 1
The artificial granite waste residue is obtained according to the following operation steps:
(a) Drying the original artificial granite waste residue at 125 ℃ to obtain crude dried waste residue with the water content of 7 parts by weight;
(b) Crushing the coarse dry waste residue into refined powder, and controlling the particle size of the powder to be 600 meshes by using a grading device;
(c) Further drying the crushed and graded powder, and controlling the water content to be 0.3 weight part for later use;
the artificial granite waste residue obtained after the operation comprises 90 to 92 mass parts of calcium carbonate, 7 to 9 mass parts of thermosetting resin, 0.1 to 0.5 mass part of pigment and 0.3 to 2 mass parts of volatile micromolecular impurities; wherein, the thermosetting resin refers to thermosetting reticular macromolecules formed by crosslinking unsaturated polyester molecules and styrene; the volatile small molecular impurities are styrene, propylene glycol, diethylene glycol, phthalic anhydride and maleic anhydride.
A processing method for filling and modifying plastic products by using artificial granite waste residues comprises the following specific operation steps:
(1) Weighing the following components in parts by mass: 100 parts of polyethylene, 20 parts of the standby artificial granite waste residue, 2 parts of stearic acid-aluminate (the weight ratio is 3/1) composite surface modifier, 0.5 part of JONCRYL ADR 4370-S produced by chain extender BASF corporation, 3 parts of Rong Jima increasing maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA) and 1 part of lubricant polyethylene wax;
(2) Mixing the artificial granite waste residue, the composite surface modifier, the chain extender and the lubricant, and performing continuous modification treatment at 80 ℃ by a powder surface modifier to obtain modified powder;
(3) Mixing the modified powder, the resin and the compatibilizer at a high speed, adding the mixture into a screw extruder, wherein the diameter of a screw is 71mm, the ratio of screw grooves is 1.5, the depth of the screw grooves is 14mm, the length-diameter ratio of the screw is 40/1, and the temperature of the screw of the co-extrusion machine is set as follows: 135/150/155/160/150/135 ℃, the screw speed is 500rpm, the extruded sample is subjected to air cooling hot cutting granulation, and then the plastic product is prepared by an injection molding machine and a film blowing machine.
The mechanical property testing method of the embodiment comprises the following steps:
the granules obtained by extrusion granulation are molded by an injection molding machine under the conditions of 170 ℃ and 45MPa to prepare dumbbell type standard tensile test sample strips, the tensile strength, the elongation at break and the bending strength are tested by an electronic universal tester, and the impact strength is tested by a cantilever beam impact tester. And (3) testing conditions are as follows: the tensile strength and the elongation at break are tested according to the standard GB/T1040.2-2006; the bending strength is tested according to the standard GB/T9341-2008, and the impact strength is tested according to the standard GB/T1043.1-2008.
The test results of this implementation are.
Tensile strength: 24.23MPa; elongation at break: 1561.58%; bending strength: 23.24MPa; impact strength: 16.50KJ/m 2 。
Example 2
In the step (1), the following components are weighed according to the mass part ratio: 100 parts of polyethylene, 30 parts of standby artificial granite waste residue, 2 parts of stearic acid-aluminate (the weight ratio is 3/1) composite surface modifier, 0.5 part of JONCRYL ADR 4370-S produced by chain extender BASF company, 3 parts of Rong Jima increasing maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA) and 1 part of lubricant polyethylene wax; the rest of the operation was the same as in example 1 (including mechanical properties testing).
The specific test results are as follows:
tensile strength: 24.33MPa; elongation at break: 1525.64%; bending strength: 23.84MPa; impact strength: 16.87KJ/m 2 。
Example 3
In the step (1), the following components are weighed according to the mass part ratio: 100 parts of polyethylene, 40 parts of standby artificial granite waste residue, 2 parts of stearic acid-aluminate (the weight ratio is 3/1) composite surface modifier, 0.5 part of JONCRYL ADR 4370-S produced by chain extender BASF company, 3 parts of Rong Jima increasing maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA) and 1 part of lubricant polyethylene wax; the rest of the operation was the same as in example 1 (including mechanical properties testing).
The specific test result is as follows:
tensile strength: 24.62MPa; elongation at break: 1509.39%; bending strength: 24.68MPa; impact strength: 17.48KJ/m 2 。
Example 4
In the step (1), the following components are weighed according to the mass part ratio: 100 parts of polyethylene, 50 parts of standby artificial granite waste residue, 2 parts of stearic acid-aluminate (the weight ratio is 3/1) composite surface modifier, 0.5 part of JONCRYL ADR 4370-S produced by chain extender BASF company, 3 parts of Rong Jima increasing maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA) and 1 part of lubricant polyethylene wax; the rest of the operation was the same as in example 1 (including mechanical properties testing).
The specific test results are as follows:
tensile strength: 25.02MPa; elongation at break: 1459.58%; bending strength: 24.75MPa; impact strength: 17.51KJ/m 2 。
Example 5
In the step (1), the following components are weighed according to the mass part ratio: 100 parts of polyethylene, 55 parts of spare artificial granite waste residue, 2 parts of stearic acid-aluminate (the weight ratio is 3/1) composite surface modifier, 0.5 part of JONCRYL ADR 4370-S produced by chain extender BASF company, 3 parts of Rong Jima increasing maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA) and 1 part of lubricant polyethylene wax; the rest of the operation was the same as in example 1 (including mechanical properties testing).
The specific test result is as follows:
tensile strength: 24.15MPa; elongation at break: 1215.53%; bending strength: 23.27Mpa; impact strength: 16.23KJ/m 2 。
Example 6
The artificial granite waste residue is obtained according to the following operation steps:
(a) Drying the original artificial granite waste residue at 135 ℃ to obtain crude dried waste residue with the water content of 5 parts by weight;
(b) Crushing the coarse dry waste residue into refined powder, and controlling the particle size of the powder to be 1200 meshes by using grading equipment;
(c) Further drying the crushed and graded powder, and controlling the water content to be 0.2 weight part for later use;
the artificial granite waste residue obtained after the operation comprises 90 to 92 mass parts of calcium carbonate, 7 to 9 mass parts of thermosetting resin, 0.1 to 0.5 mass part of pigment and 0.3 to 2 mass parts of volatile micromolecular impurities; wherein, the thermosetting resin refers to thermosetting reticular macromolecules formed by crosslinking unsaturated polyester molecules and styrene; the volatile small molecular impurities are styrene, propylene glycol, diethylene glycol, phthalic anhydride and maleic anhydride.
A processing method for filling and modifying plastic products by using artificial granite waste residues comprises the following specific operation steps:
(1) Weighing the following components in parts by mass: 100 parts of polyvinyl chloride, 15 parts of the standby artificial granite waste residue, 0.2 part of stearic acid-titanate (the weight ratio is 4/1) composite surface modifier, 0.5 part of JONCRYL ADR 4400.5 part produced by chain extender BASF company, 0.2 part of Rong Jima maleic anhydride grafted ethylene-octene copolymer (MAH-g-POE) and 1.5 parts of lubricant paraffin;
(2) Mixing the artificial granite waste residue, the composite surface modifier, the chain extender and the lubricant, and performing continuous modification treatment at 90 ℃ by a powder surface modifier to obtain modified powder;
(3) Mixing the modified powder, the resin and the compatibilizer at a high speed, adding the mixture into a screw extruder, wherein the diameter of a screw is 71mm, the ratio of screw grooves is 1.5, the depth of the screw grooves is 14mm, the length-diameter ratio of the screw is 40/1, and the temperature of the screw of the co-extrusion machine is set as follows: 165/175/180/190/180/175 ℃, the screw speed is 500rpm, the mixture is extruded, and the extruded sample is subjected to air cooling hot cutting granulation, and then is subjected to injection molding machine and film blowing machine to prepare the plastic product.
The mechanical property testing method of the embodiment comprises the following steps:
the granules obtained by extrusion granulation are molded by an injection molding machine under the conditions of 190 ℃ and 45MPa to prepare dumbbell type standard tensile test sample strips, the tensile strength, the elongation at break and the bending strength are tested by an electronic universal tester, and the impact strength is tested by a cantilever beam impact tester. And (3) testing conditions are as follows: the tensile strength and the elongation at break are tested according to the standard GB/T1040.2-2006; the bending strength is tested according to the standard GB/T9341-2008, and the impact strength is tested according to the standard GB/T1043.1-2008.
The test results of this implementation are.
Tensile strength: 14.38MPa; elongation at break: 88.89 percent; bending strength: 9.24MPa; impact strength: 52.54KJ/m 2 。
Example 7
The artificial granite waste residue is obtained according to the following operation steps:
(a) Drying the original artificial granite waste residue at 105 ℃ to obtain crude dried waste residue with the water content of 5 parts by weight;
(b) Crushing the coarse dry waste residue into refined powder, and controlling the particle size of the powder to be 400 meshes by using classification equipment;
(c) Further drying the crushed and classified powder, and controlling the water content to be 0.3 weight part for later use;
the artificial granite waste residue obtained after the operation comprises 90 to 92 mass parts of calcium carbonate, 7 to 9 mass parts of thermosetting resin, 0.1 to 0.5 mass part of pigment and 0.3 to 2 mass parts of volatile micromolecular impurities; wherein, the thermosetting resin refers to thermosetting reticular macromolecules formed by crosslinking unsaturated polyester molecules and styrene; the volatile small molecular impurities are styrene, propylene glycol, diethylene glycol, phthalic anhydride and maleic anhydride.
A processing method for filling modified plastic products by using artificial granite waste residues comprises the following specific operation steps:
(1) Weighing the following components in parts by mass: 100 parts of polypropylene, 45 parts of the prepared artificial granite waste residue, 15 parts of stearic acid-boric acid ester composite surface modifier, 0.1 part of JONCRYL ADR 4368-C produced by chain extender BASF company, 4 parts of maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer (MAH-g-SEBS) as a compatibilizer and 2 parts of ethylene bis stearamide as a lubricant;
(2) Mixing the artificial granite waste residue, the composite surface modifier, the chain extender and the lubricant, and performing continuous modification treatment at 100 ℃ by a powder surface modifier to obtain modified powder;
(3) Mixing the modified powder, the resin and the compatibilizer at a high speed, adding the mixture into a screw extruder, wherein the diameter of a screw is 71mm, the ratio of screw grooves is 1.5, the depth of the screw grooves is 14mm, the length-diameter ratio of the screw is 40/1, and the temperature of the screw of the co-extrusion machine is set as follows: 185/195/205/200/190/185 ℃ and 500rpm, extruding, and carrying out air cooling hot cutting granulation on an extruded sample, and then carrying out injection molding and film blowing to prepare the plastic product.
The mechanical property testing method of the embodiment comprises the following steps:
the granules obtained by extrusion granulation are subjected to injection molding by an injection molding machine under the conditions of 210 ℃ and 45MPa to prepare dumbbell type standard tensile test sample strips, the tensile strength, the elongation at break and the bending strength are tested by an electronic universal testing machine, and the impact strength is tested by a cantilever beam impact tester. And (3) testing conditions are as follows: the tensile strength and the elongation at break are tested according to the standard GB/T1040.2-2006; the bending strength is tested according to the standard GB/T9341-2008, and the impact strength is tested according to the standard GB/T1043.1-2008.
The test results of this implementation are.
Tensile strength: 28.76MPa; elongation at break: 838.57%; bending strength: 43.87MPa; impact strength: 8.54KJ/m 2 。
Example 8
The artificial granite waste residue is obtained according to the following operation steps:
(a) Drying the original artificial granite waste residue at 110 ℃ to obtain crude dried waste residue with the water content of 8 parts by weight;
(b) Crushing the coarse dry waste residue into refined powder, and controlling the particle size of the powder to be 300 meshes by using grading equipment;
(c) Further drying the crushed and graded powder, and controlling the water content to be 0.6 weight part to obtain the powder for later use;
the artificial granite waste residue obtained after the operation comprises 90 to 92 mass parts of calcium carbonate, 7 to 9 mass parts of thermosetting resin, 0.1 to 0.5 mass part of pigment and 0.3 to 2 mass parts of volatile micromolecular impurities; wherein, the thermosetting resin refers to thermosetting reticular macromolecules formed by crosslinking unsaturated polyester molecules and styrene; the volatile small molecular impurities are styrene, propylene glycol, diethylene glycol, phthalic anhydride and maleic anhydride.
A processing method for filling and modifying plastic products by using artificial granite waste residues comprises the following specific operation steps:
(1) Weighing the following components in parts by mass: 100 parts of acrylonitrile-butadiene-styrene terpolymer, 35 parts of the spare artificial granite waste residue, 12 parts of stearic acid-aluminate (the weight ratio is 4/1) composite surface modifier, 2.5 parts of chain extender JONCRYL ADR 4370-F, 1 part of compatibilizer maleic anhydride grafted styrene-ethylene-butylene-styrene block copolymer (MAH-g-SEBS) and 2 parts of lubricant stearic acid amide;
(2) Mixing the artificial granite waste residue, the composite surface modifier, the chain extender and the lubricant, and performing continuous modification treatment at 500 ℃ by a powder surface modifier to obtain modified powder;
(3) Mixing the modified powder, the resin and the compatibilizer at a high speed, adding the mixture into a screw extruder, wherein the diameter of a screw is 71mm, the ratio of screw grooves is 1.5, the depth of the screw grooves is 14mm, the length-diameter ratio of the screw is 40/1, and the temperature of the screw of the co-extrusion machine is set as follows: 215/225/235/230/220/215 ℃ and the screw speed is 500rpm, extruding, and carrying out air cooling hot cutting granulation on an extruded sample, and then carrying out injection molding and film blowing to prepare the plastic product.
The mechanical property testing method of the embodiment comprises the following steps:
the granules obtained by extrusion granulation are molded by an injection molding machine under the conditions of 240 ℃ and 45MPa to prepare dumbbell type standard tensile test sample strips, the tensile strength, the elongation at break and the bending strength are tested by an electronic universal testing machine, and the impact strength is tested by a cantilever beam impact tester. And (3) testing conditions are as follows: testing the tensile strength and the elongation at break according to the reference standard GB/T1040.2-2006; the bending strength is tested according to the standard GB/T9341-2008, and the impact strength is tested according to the standard GB/T1043.1-2008.
The test results of this implementation are.
Tensile strength: 59.66MPa; elongation at break: 43.56 percent; bending strength: 83.18MPa; impact strength: 178.24KJ/m 2 。
Comparative example 1
In the step (1), the following components are weighed according to the mass part ratio: 100 parts of polyethylene, 20 parts of artificial granite waste residue, 2 parts of aluminate and 1 part of lubricant polyethylene wax; the rest of the operation was the same as in example 1 (including mechanical properties testing).
The specific test result is as follows:
tensile strength: 18.38MPa; elongation at break: 859.64%; bending strength: 19.27MPa; impact strength: 10.38KJ/m 2 。
Comparative example 2
In the step (1), the following components are weighed according to the mass part ratio: 100 parts of polyethylene, 20 parts of artificial granite waste residue, 2 parts of stearic acid-aluminate (weight ratio is 3/1) composite surface modifier and 1 part of lubricant polyethylene wax; the rest of the operation was the same as in example 1 (including mechanical properties testing).
The specific test result is as follows:
tensile strength: 19.48MPa; elongation at break: 1094.27%; bending strength: 19.97MPa; impact strength: 11.06KJ/m 2 。
Comparative example 3
In the step (1), the following components are weighed according to the mass part ratio: 100 parts of polyethylene, 20 parts of artificial granite waste residue, 2 parts of aluminate, 0.5 part of JONCRYL ADR 4370-S produced by chain extender BASF company and 1 part of lubricant polyethylene wax; the rest of the operation was the same as in example 1 (including mechanical properties testing).
The specific test result is as follows:
tensile strength: 22.79MPa; elongation at break: 1254.41%; bending strength: 22.38MPa; impact strength: 14.18KJ/m 2 。
Comparative example 4
In the step (1), the following components are weighed according to the mass part ratio: 100 parts of polyethylene, 20 parts of artificial granite waste residue, 2 parts of aluminate, 3 parts of maleic anhydride grafted ethylene-vinyl acetate copolymer (MAH-g-EVA) as a compatibilizer and 1 part of polyethylene wax as a lubricant; the rest of the operation was the same as in example 1 (including mechanical properties testing).
The specific test result is as follows:
tensile strength: 22.69MPa; elongation at break: 1373.35%; bending strength: 22.97MPa; impact strength: 13.82KJ/m 2 。
From comparative examples 1-4, it can be seen from the results of example 1 that, in the composite material of the present invention, the mechanical performance indexes such as tensile strength, elongation at break, flexural strength, impact strength, etc. are improved to different degrees after the stearic acid-aluminate (weight ratio is 3/1) composite surface modifier, basf JONCRYL ADR 4370-S chain extender, and maleic anhydride grafted ethylene-vinyl acetate copolymer compatibilizer are added to the material mixture ratio of comparative example 1. After the stearic acid-aluminate (the weight ratio is 3/1) composite surface modifier, the BASF JONCRYL ADR 4370-S chain extender and the maleic anhydride grafted ethylene-vinyl acetate copolymer compatibilizer are synthesized, all the auxiliary agents can play a synergistic effect, so that better comprehensive performance is obtained.
As can be seen from figures 1 and 2, the plastic product obtained by the invention has almost integrated artificial granite waste residue and matrix resin, and no obvious gap or hole is observed between the artificial granite waste residue and the matrix resin, which shows that the invention can effectively improve the interface compatibility between the artificial granite waste residue and the matrix resin compared with comparative examples 1-4.
The statistics of the mechanical properties of the plastic articles of the above examples 1-5 and comparative examples 1-4 are shown in Table 1:
TABLE 1 mechanical Properties of examples 1 to 5 and comparative examples 1 to 4
The artificial granite waste residue of the invention is a high-compactness material formed by crosslinking and curing calcium carbonate powder and unsaturated resin after fully mixing, and the outer surface of calcium carbonate particles in most of the artificial granite waste residue is tightly coated by reticular thermosetting unsaturated resin, and is a complex of inorganic particles and organic substances. Therefore, the calcium carbonate powder is blended and modified with polymer resin, on one hand, part of the calcium carbonate powder is required to be completely coated by thermosetting unsaturated resin, and the surface of the exposed calcium carbonate powder is organically modified, so that the purpose of organically modifying the calcium carbonate powder can be achieved by adding surface modifiers such as aluminate, titanate, borate, stearic acid and the like; on the other hand, after the artificial granite waste residue is dried, the content of the unsaturated resin is as high as 7-9 parts by mass (general coupling modification, the dosage of the coupling agent is about 2% of the weight of the powder, and the activation index can reach about 90%), which shows that the calcium carbonate powder coated by the unsaturated resin accounts for the vast majority of the waste residue, so the compatibility between the thermosetting resin and the composite matrix resin on the surface of the artificial granite waste residue is improved by considering the interface effect between the thermosetting resin and the composite matrix resin, and the purpose can be achieved by adding a compatibilizer. The compatibilizer is also called compatilizer, and refers to an aid which promotes two incompatible polymers to be combined into a whole by virtue of intermolecular bonding force so as to obtain a stable blend.
In addition, according to the analysis of the preparation process of the artificial granite, the artificial granite needs to be cured by heating after mixing, stirring, compression molding and the like of calcium carbonate powder and resin. Unsaturated polyester molecules and styrene molecules are fixed on various parts of the artificial stone raw materials before curing and lack of fluidity among the unsaturated polyester molecules and the styrene molecules, which inevitably results in residual parts of unreacted components or partial insufficiently reacted active groups in the artificial granite waste residues. Therefore, when blending and modifying with polymer resin, a small amount of chain extender with reactivity is added to further link the residual active ingredients, thereby improving the comprehensive performance of the composite material. Among them, the chain extender, also called chain extender, is a substance that can react with functional groups on the linear polymer chain to expand the molecular chain and increase the molecular weight, and is commonly used to improve the mechanical properties and the processing properties of products such as polyurethane, polyester, etc.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (5)
1. A plastic product filled and modified by using artificial granite waste residue is characterized by comprising the following components in parts by mass: 100 parts of resin, 15 to 500 parts of artificial granite waste residue, 0.2 to 15 parts of surface modifier, 0.1 to 5 parts of chain extender, 0.2 to 4 parts of compatibilizer and 0.3 to 2 parts of lubricant;
wherein the resin is at least one of polyethylene, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene terpolymer or polylactic acid; the lubricant is at least one of stearic acid amide, ethylene bis-stearic acid amide, paraffin, polyethylene wax or low molecular weight polypropylene;
wherein the surface modifier is at least one of stearic acid-aluminate, stearic acid-titanate or stearic acid-borate composite surface modifier; wherein, the weight ratio of stearic acid in the composite surface modifier is more than 50 percent;
wherein the chain extender is a JONCRYL ADR series product produced by BASF company;
wherein the compatibilizer is at least one of ethylene-methyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene-diene monomer rubber, ethylene-octene copolymer, styrene-ethylene-butene-styrene block copolymer, maleic anhydride grafted ethylene-vinyl acetate copolymer, maleic anhydride grafted ethylene-octene copolymer, maleic anhydride grafted ethylene-propylene-diene monomer rubber and maleic anhydride grafted styrene-ethylene-butene-styrene block copolymer;
wherein the artificial granite waste residue is obtained according to the following operation steps:
(a) Drying the original artificial granite waste residue at 60-135 ℃ to obtain crude dried waste residue with the water content of 5~8 parts by weight;
(b) Crushing the coarse dry waste residue into refined powder, and controlling the particle size of the powder to be 300 to 1200 meshes by using grading equipment;
(c) Further drying the crushed and graded powder, and controlling the water content to be less than 0.7 weight part to obtain the nano-composite material;
the artificial granite waste residue obtained after the operation comprises 90 to 92 mass parts of calcium carbonate, 7~9 mass parts of thermosetting resin, 0.1 to 0.5 mass part of pigment and 0.3 to 2 mass parts of volatile small molecular impurities; the thermosetting resin is a thermosetting reticular macromolecule formed by crosslinking unsaturated polyester molecules and styrene; the volatile small molecular impurities are styrene, propylene glycol, diethylene glycol, phthalic anhydride and maleic anhydride.
2. A plastic article according to claim 1, wherein: the surface modifier is stearic acid-aluminate composite surface modifier.
3. A plastic article according to claim 1, wherein: the chain extender is JONCRYL ADR 4370-S produced by BASF corporation.
4. A plastic article according to claim 1, wherein: the compatibilizer is maleic anhydride grafted ethylene propylene diene monomer.
5. The method for processing plastic products filled and modified by artificial granite waste slag as claimed in claim 1, characterized in that it comprises the following steps:
(1) Weighing the following components in parts by mass: 100 parts of resin, 15 to 500 parts of artificial granite waste residue, 0.2 to 15 parts of surface modifier, 0.1 to 5 parts of chain extender, 0.2 to 4 parts of compatibilizer and 0.3 to 2 parts of lubricant;
(2) Mixing the artificial granite waste residue, a surface modifier, a chain extender and a lubricant, and carrying out continuous modification treatment at 50-110 ℃ to obtain modified powder;
(3) And mixing the modified powder, the resin and the compatibilizer, extruding and granulating, and then preparing the plastic product by injection molding and film blowing.
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| CN112374804B (en) * | 2020-11-19 | 2022-05-24 | 贺州学院 | Styrene-free bulk molding compound based on artificial granite waste residues and preparation method thereof |
| CN113235180A (en) * | 2021-04-23 | 2021-08-10 | 中国科学院过程工程研究所 | Method for preparing polyester staple fibers by using artificial granite waste |
| CN113278306A (en) * | 2021-05-12 | 2021-08-20 | 广西科学院 | Microwave wet-method modified artificial granite waste residue and recycling process method thereof |
| CN113185816A (en) * | 2021-05-21 | 2021-07-30 | 贺州学院 | Polymer/artificial stone waste residue composite film material and preparation method thereof |
| CN114957832B (en) * | 2022-05-23 | 2023-09-26 | 海南蓝岛环保产业股份有限公司 | Polyethylene composite material filled with artificial marble waste residues |
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