WO2022110593A1 - 一种耐磨耐老化家具塑料颗粒及制备方法 - Google Patents

一种耐磨耐老化家具塑料颗粒及制备方法 Download PDF

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WO2022110593A1
WO2022110593A1 PCT/CN2021/083284 CN2021083284W WO2022110593A1 WO 2022110593 A1 WO2022110593 A1 WO 2022110593A1 CN 2021083284 W CN2021083284 W CN 2021083284W WO 2022110593 A1 WO2022110593 A1 WO 2022110593A1
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resistant
aging
parts
weight
wear
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PCT/CN2021/083284
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English (en)
French (fr)
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胡森川
杨曦
罗万象
陈志益
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胡森川
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the invention belongs to the technical field of plastic functionalization, relates to a plastic used for furniture, and further relates to a wear-resistant and aging-resistant furniture plastic particle and a preparation method.
  • plastics As a bulk raw material for current production, living and industrial supplies, plastics not only involve a wide range of fields, but also have a wide variety of types. Especially with the continuous improvement of the functionality of polymer plastics, it has played a huge role in replacing metal and wood. Therefore, the use of plastics for furniture production has been rapidly developed. Compared with traditional solid wood furniture, rattan furniture, wrought iron furniture, etc., plastic furniture is a new type of furniture. It is popular with consumers because of its bright colors, different shapes, lightness and compactness, wide application and easy maintenance.
  • Plastic has the advantages of light weight, stable chemical properties, no rust, good impact resistance, good transparency, good insulation, good colorability and low processing costs, and can be well shaped for making furniture. , thereby reducing the use of a large amount of adhesives for wooden furniture, and has outstanding contributions to environmental protection. Compared with furniture made of wood or metal materials, plastic furniture is extremely malleable and can be processed into any shape. At the same time, it is rich in color and can be cleverly matched with other furniture to beautify the room.
  • Chinese invention patent CN107523007A discloses a wear-resistant plastic composite board with excellent performance, which belongs to the technical field of plastic products. It is prepared from the following components in parts by weight: 40-60 parts of polyoxymethylene plastic, 20-30 parts of acrylonitrile-butadiene-styrene copolymer, 15-30 parts of polymethacrylate, and 5 parts of polylactic acid. ⁇ 10 parts, 1-5 parts of antioxidant, 5-8 parts of anti-wear agent, 10-18 parts of filler, 1-5 parts of anti-aging agent, 1-3 parts of lubricant, 2-5 parts of anti-corrosion resin, carbonized 5 to 8 parts of silicon crystal grains.
  • the plastic plate prepared by the invention has excellent wear resistance, high mechanical strength, strong corrosion resistance, high temperature resistance, improved oxidation resistance and weather resistance, greatly increased service life, and has a broad market space.
  • Chinese invention patent CN111019311A discloses a wear-resistant engineering plastic and its preparation method, which is composed of the following materials in parts by weight: 65-75 parts of unsaturated polyester, 60-80 parts of polyethylene terephthalate, semi-aromatic 15-35 parts of family nylon PA6T, 10-12 parts of polytetrafluoroethylene, 10-20 parts of potassium titanate whisker reinforcement, 3-5 parts of butyl tin mercaptide stabilizer, 1-5 parts of additives, 0.6-1.8 parts of coupling agent parts, 0.2-0.5 parts of antioxidants and 0.7-2.5 parts of lubricants, wherein the lubricants are one or more compositions of liquid paraffin, polyethylene wax and glycerol monostearate, the invention relates to engineering plastics product technology In the field of wear-resistant engineering plastics and the preparation method thereof, the raw materials and ingredients are reasonable, and the engineering plastics produced have obvious and durable wear-resistant effects, excellent mechanical properties, and better effects when used in conjunction with polytetrafluor
  • the present invention aims to develop a plastic particle with wear resistance and aging resistance, which can be directly used in various injection molding, Processing of extruded sheets, etc., for plastic furniture.
  • the present invention provides a method for preparing wear-resistant and aging-resistant furniture plastic particles, characterized in that: the specific preparation method is as follows:
  • polypropylene, compatibilizer, coupling agent, filler, and toner are weighed according to parts by weight: 70-80 parts by weight of polypropylene, 1-2 parts by weight of compatibilizer, 0.1-0.2 parts by weight of coupling agent, 3-5 parts by weight of filler, toner 0-1 parts by weight.
  • the materials in the silo B and the silo C are automatically weighed and mixed at a mass ratio of 1:8-10, and then sent to the first feeding of the screw extruder through the automatic elevator; the material in the silo A is added to the screw
  • the second feeding port of the extruder the temperature of the screw extruder is set to: 160-180°C for the first stage, 190-200°C for the second stage, 210-220°C for the third stage, 230-225°C for the fourth stage,
  • the fifth section is 160-180°C; the first feeding port is set in the first section, the second feeding port is set between the third section and the fourth section, and the distance between the first feeding port and the second feeding port is controlled at 65-85cm; Extruded through a screw extruder, air-cooled and diced, vibrated and screened, and packaged to obtain a wear-resistant and aging-resistant furniture plastic granule.
  • Nano inorganic powder has a certain strengthening effect when used in polymer plastics, and nano inorganic powder will also increase the wear resistance of plastics. However, if it cannot be effectively dispersed, the interface enhancement effect and resistance of nano inorganic powder in plastics Grinding effect will be limited. How to effectively and uniformly disperse nano-inorganic powders in plastics is a major problem for technicians. Since the processing of plastics is in a thermoplastic viscoelastic state, it is obviously difficult to directly disperse nano-inorganic powders in them. In the liquid state, the dispersion effect of the nano-inorganic powder is good.
  • the nano-inorganic powder and the paraffin are formed in a weight ratio of 1:5-8 to form a liquid state.
  • High-speed stirring is conducive to the dispersion of nano-inorganic powders.
  • the mass ratio of the nano inorganic powder and the silicone is 100:0.5-1; by grinding and dispersing the silicone powder, on the one hand, the large particles agglomerated by the nano inorganic powder are depolymerized and dispersed, On the other hand, nano-inorganic powder has lipophilicity and is easy to disperse in molten paraffin; in addition, silicone powder is beneficial to improve wear resistance and scratch resistance.
  • paraffin wax is used in a weight ratio of 1:5-8, more paraffin is used to form a liquid, and high-speed stirring in the liquid state is conducive to the dispersion of nano-inorganic powder.
  • the nano inorganic powder described in step (1) selects one or more of nano calcium carbonate, nano precipitated barium sulfate, nano mica powder, nano montmorillonite, nano talc, nano diatomite, nano kaolin combination of species.
  • step (1) can be achieved by using mature ball milling and jet milling.
  • the temperature adopted makes the paraffin melting as the criterion, and the temperature is not easy to be too high, and the excessively high temperature can cause the paraffin to volatilize and deteriorate;
  • selecting 58 #Paraffin wax can be heated in a constant temperature stirring tank in an oil bath at 70°C.
  • a stirring speed of 800-1000 rpm is used for stirring for 20-30 min.
  • the amount of inorganic fibers added in step (2) is 15-20% of the mass of the nanoparticle pre-dispersion; the amount of plant fiber powder added is 15-20% of the mass of the nanoparticle pre-dispersion.
  • Inorganic fibers and plant fiber powders can not only increase the impact strength of plastics, but also increase the wear resistance of plastics and prevent the prepared plastic furniture from scratching; similarly, inorganic fibers and plant fiber powders are difficult to directly disperse in viscoelastic plastics.
  • inorganic fibers and plant fiber powder are dispersed in the liquid nanoparticle pre-dispersion liquid in advance, and the purpose is to make them easily dispersed in viscoelastic plastics during screw extrusion.
  • the inorganic fibers described in step (2) are preferably at least one of glass fibers, aluminum silicate fibers, wollastonite fibers, brucite fibers, sepiolite fibers, calcium carbonate whiskers, and calcium sulfate whiskers. kind.
  • the plant fiber powder described in step (2) is one of corn stalks, wheat stalks, and flax stalks that have passed through a 50-mesh screen. Further, we found through a large number of experiments that the addition of flax straw powder has a more significant effect on improving the wear resistance of plastics. The addition of the plant fiber powder makes the furniture prepared from the obtained plastic particles have a certain woody feel.
  • step (3) POE, antioxidant and ultraviolet absorber are granulated to prepare composite anti-aging agent in advance, POE has good anti-aging properties, and composite anti-aging agent is formed by pre-forming with antioxidant and ultraviolet absorber When mixed with polypropylene, POE has better elasticity and ductility, so that antioxidants and ultraviolet absorbers can form protection between polypropylene and polypropylene in the mixture, and promote the anti-aging effect.
  • the antioxidant in step (3) is selected from one of 1010, DLTP, and BHT; the ultraviolet absorber is selected from UV-531.
  • the grade of polypropylene selected in step (4) is at least one of EPF30R, EPR30R and EPS30R; the compatibilizer is polypropylene grafted maleic anhydride; the coupling agent is titanate coupling A kind of agent and aluminate coupling agent; the filler is selected from one of glass microbeads and serpentine powder; on the one hand, it can assist the processing fluidity of plastics, and on the other hand, it can assist in improving the wear resistance of plastics
  • the color powder is selected according to the specific color needs, and it can be a pigment or a commercially available color masterbatch; the present invention recommends choosing titanium dioxide for white color, mica titanium pearlescent pigment, iron red and iron orange for pearlescent color. , iron yellow, zinc iron yellow, etc., pigments containing heavy metals such as chrome green, chrome yellow, medium chrome yellow, molybdenum chrome red, cadmium yellow, cadmium orange, cadmium red, etc. are not recommended.
  • the material added to the second feeding port in step (5) is 15-20% of the mass of the material added to the first feeding port.
  • the material melted and kneaded in the second feeding port is mixed with the pre-dispersed pre-mixed material, the pre-prepared material is easy to melt and disperse, and quickly disperse in the molten in the mix.
  • the present invention firstly adds the materials in the B and C silos to melt kneading at the first feeding port, and adds the pre-dispersed material A to the completely melted second feeding port, thereby promoting the good dispersion of the pre-dispersed material A. Further preferably, the distance between the first feeding port and the second feeding port is controlled at 80 cm.
  • the screw extruder in step (5) is a co-rotating twin-screw extruder, and the co-rotating twin-screw extruder has a better shear dispersion effect, and as a preference, it is beneficial to the dispersion of nano-inorganic substances.
  • the rotational speed of the screw extruder is controlled to be 150-200 rpm, and the pelletizing adopts an air-cooled die face for pelletizing.
  • the present invention provides a kind of wear-resistant and anti-aging furniture plastic particles prepared by the above method.
  • polypropylene has low cost and is easy to be processed into large pieces of furniture or furniture panels by injection molding, extrusion and other processes.
  • polypropylene has lower rigidity when used in furniture. , The strength is low, the prepared furniture is not wear-resistant, easy to be scratched, and the aging phenomenon is obvious. Therefore, the present invention comprehensively modifies polypropylene for the needs of plastic furniture, and improves the abrasion resistance and aging resistance of polypropylene in accordance with the national standard "General Technical Conditions for Plastic Furniture" (GB/T3487-2016).
  • nano inorganic powder and silicone are ground and dispersed in advance, dispersed in molten paraffin to form a liquid state, and nano inorganic powder is dispersed by liquid dispersion; meanwhile, inorganic fibers and plant fibers that are difficult to disperse are pre-dispersed in liquid paraffin wax.
  • POE has good aging resistance.
  • POE has better elasticity and ductility when it is mixed with polypropylene, so that antioxidants and ultraviolet absorbers can be absorbed.
  • the agent is evenly dispersed with polypropylene in the mixture to form protection and promote the anti-aging effect.
  • the present invention makes the pre-dispersed liquid paraffin of nano inorganic powder, inorganic fiber and plant fiber, and adds it in the second feeding port where polypropylene is completely melted to increase the dispersibility and improve the Abrasion resistance of plastics.
  • the present invention utilizes the good aging resistance and ductility of POE, and forms a composite anti-aging agent with antioxidants and ultraviolet absorbers in advance.
  • the elasticity and ductility of POE make the antioxidants .
  • the UV absorber is uniformly dispersed with polypropylene in the mixing material to form protection, and the dispersion effect is better than that of directly adding antioxidant and UV absorber to polypropylene dispersion.
  • the obtained plastic particles not only have good impact resistance, but also wear resistance and aging resistance when used in furniture, and can directly prepare furniture by injection molding or extrusion. Preparation of furniture into panels.
  • the materials in the silo B and the silo C are automatically weighed and mixed at a mass ratio of 1:8, and then sent to the first feeding of the co-rotating twin-screw extruder through the automatic elevator; the material in the silo A is added
  • the second feeding port of the screw extruder; the material added to the second feeding port is 20% of the mass of the material added to the first feeding port.
  • the third stage is 210 °C
  • the fourth stage is 225 °C
  • the fifth stage is 180 °C
  • the first feeding port is set in the first section, the second feeding port is set between the third and fourth sections, and the first feeding port is connected to the second feeding port.
  • the distance of the mouth is controlled at 80cm; the speed of the screw is controlled at 150rpm; it is extruded through a co-rotating twin-screw extruder, diced on an air-cooled die surface, vibrated, sieved, and packaged to obtain a wear-resistant and aging-resistant furniture plastic granule.
  • the materials in the silo B and the silo C are automatically weighed and mixed at a mass ratio of 1:8, and then sent to the first feeding of the co-rotating twin-screw extruder through the automatic elevator; the material in the silo A is added
  • the second feeding port of the screw extruder; the material added to the second feeding port is 20% of the mass of the material added to the first feeding port;
  • the temperature of the screw extruder is set as: the first section 160 ° C, the second section 190 ° C,
  • the third section is 210 °C, the fourth section is 225 °C, and the fifth section is 180 °C;
  • the first feeding port is located in the first section, the second feeding port is set between the third and fourth sections, and the first feeding port is
  • the distance of the feeding port is controlled at 80cm; the screw speed is controlled at 150rpm; extruded through a co-rotating twin-screw extruder, air-cooled die face granulation, vibrating screening,
  • the materials in the silo B and the silo C are automatically weighed and mixed at a mass ratio of 1:10, and then sent to the first feeding of the co-rotating twin-screw extruder through the automatic elevator; the material in the silo A is added
  • the second feeding port of the screw extruder; the material added to the second feeding port is 18% of the mass of the material added to the first feeding port;
  • the temperature of the screw extruder is set to: 160 ° C for the first section, 200 ° C for the second section,
  • the third section is 210 °C, the fourth section is 225 °C, and the fifth section is 180 °C;
  • the first feeding port is located in the first section, the second feeding port is set between the third and fourth sections, and the first feeding port is
  • the distance of the feeding port is controlled at 80cm; the rotation speed is controlled at 150rpm; extruded through a co-rotating twin-screw extruder, air-cooled die surface dicing, vibrating
  • the materials in the silo B and the silo C are automatically weighed and mixed at a mass ratio of 1:10, and then sent to the first feeding of the co-rotating twin-screw extruder through the automatic elevator; the material in the silo A is added
  • the second feeding port of the screw extruder; the material added to the second feeding port is 18% of the mass of the material added to the first feeding port;
  • the temperature of the screw extruder is set to: 160 ° C for the first section, 200 ° C for the second section,
  • the third section is 210 °C, the fourth section is 225 °C, and the fifth section is 180 °C;
  • the first feeding port is located in the first section, the second feeding port is set between the third and fourth sections, and the first feeding port is
  • the distance of the feeding port is controlled at 80cm; the rotation speed is controlled at 150rpm; extruded through a co-rotating twin-screw extruder, air-cooled die surface dicing, vibrating
  • the materials in the silo B and the silo C are automatically weighed and mixed at a mass ratio of 1:8, and then sent to the first feeding of the co-rotating twin-screw extruder through the automatic elevator; the material in the silo A is added
  • the second feeding port of the screw extruder; the material added to the second feeding port is 16% of the mass of the material added to the first feeding port;
  • the temperature of the screw extruder is set to: 180 ° C for the first section, 200 ° C for the second section,
  • the third section is 210 °C, the fourth section is 225 °C, and the fifth section is 170 °C;
  • the first feeding port is set in the first section, the second feeding port is set between the third and fourth sections, and the first feeding port is
  • the distance of the feeding port is controlled at 80cm; the rotation speed is controlled at 200rpm; extruded through a co-rotating twin-screw extruder, granulated on the air-cooled die
  • the materials in the silo B and the silo C are automatically weighed and mixed at a mass ratio of 1:8, and then sent to the first feeding of the co-rotating twin-screw extruder through the automatic elevator; the material in the silo A is added
  • the second feeding port of the screw extruder; the material added to the second feeding port is 16% of the mass of the material added to the first feeding port;
  • the temperature of the screw extruder is set to: 180 ° C for the first section, 200 ° C for the second section,
  • the third section is 210 °C, the fourth section is 225 °C, and the fifth section is 170 °C;
  • the first feeding port is set in the first section, the second feeding port is set between the third and fourth sections, and the first feeding port is
  • the distance of the feeding port is controlled at 80cm; the rotation speed is controlled at 200rpm; extruded through a co-rotating twin-screw extruder, granulated on the air-cooled die
  • the materials in the silo B and the silo C are automatically weighed and mixed at a mass ratio of 1:8, and then sent to the first feeding of the co-rotating twin-screw extruder through the automatic elevator; the material in the silo A is added
  • the second feeding port of the screw extruder; the material added to the second feeding port is 20% of the mass of the material added to the first feeding port;
  • the temperature of the screw extruder is set to: 180 ° C for the first section, 200 ° C for the second section,
  • the third section is 210 °C, the fourth section is 225 °C, and the fifth section is 170 °C;
  • the first feeding port is set in the first section, the second feeding port is set between the third and fourth sections, and the first feeding port is
  • the distance of the feeding port is controlled at 80cm; the rotation speed is controlled at 200rpm; extruded through a co-rotating twin-screw extruder, granulated on the air-cooled die surface
  • the fourth stage is 225 °C
  • the fifth stage is 170 °C
  • the control speed is 200rpm; extruded through a co-rotating twin-screw extruder, air-cooled die surface granulation, vibrating screening, and packaging to obtain a wear-resistant and aging-resistant furniture plastic granules .
  • the plastic granules obtained in Examples 1-4 and Comparative Examples 1-4 were injection-molded into plates with a thickness of 4 mm, and then cut into samples with a width of 10 mm and a length of 80 mm for impact strength testing.
  • GB/T1043.1-2008 Determination of Impact Properties of Plastic Simply Supported Beams Part 1 to test; further, the obtained sheet with a thickness of 4 mm is subjected to xenon light exposure for aging treatment, referring to GB/T16422.2-2014 (Plastic Laboratory Light Source Exposure Test method), in order to simulate sunlight, the xenon arc lamp was filtered by a filter, and the exposure cycle was carried out according to the method A, cycle number 1, and the impact strength was tested after irradiating for 500 h, and the aging resistance was evaluated by the change of the impact strength before and after illumination.
  • the impact strength of the samples before and after the xenon arc lamp irradiation is shown in Table 1.
  • the plastic particles obtained by Example 1-4 and Comparative Example 1-4 are injection-molded into a plate with a smooth surface thickness of 4 mm, with reference to GB/T 6739-2006 (paint and varnish pencil method is used to measure paint film hardness), using different hardnesses
  • the pencil starts to scratch the surface of the plastic plate from 3B, and gradually increases the hardness of the pencil until scratches are made, so as to measure the wear resistance and scratch resistance of the plate. As shown in Table 1.
  • the plastic particles obtained by the present invention have excellent aging resistance, and the impact strength retention after 500h of xenon lamp illumination is greater than 85%, exceeding the mild retention rate specified in GB/T3487-2016 (general technical conditions for plastic furniture) greater than 60% , to meet the needs of furniture production.
  • the scratch test is carried out by using pencils with different hardness, and the product prepared from the plastic of the present invention has high hardness, scratch resistance and good wear resistance.
  • Comparative example 1 reduces the amount of paraffin when dispersing the nano-inorganic powder. Due to the reduction in the amount of paraffin, the nano-inorganic powder is not dispersed in a liquid state, and its dispersion is affected. In the present invention, it is manifested that the nanoparticles fail to establish an effective interface. Wear resistance, while its nano-enhancing function is also greatly reduced.
  • Comparative example 2 does not add silicone powder to treat nano-precipitated barium sulfate, which has a certain influence on the dispersibility of barium sulfate and the compatibility with polypropylene, and silicone powder is used in plastics because it has scratch resistance, so it is not suitable for polypropylene. wear resistance has a certain impact.
  • Comparative Example 3 In Comparative Example 3, POE, antioxidant BHT, and ultraviolet absorber UV-531 were not melt-mixed and dispersed with a screw, but were directly mixed with powder for use, so that the antioxidant and ultraviolet absorber were mixed with polypropylene uniformly. Deterioration, affecting the absorption of ultraviolet light by the ultraviolet absorber and affecting the aging resistance.
  • Comparative Example 4 material A was not added at the second feeding port, that is, it was not added when polypropylene was completely melted. Initially, the viscosity was too large, making it difficult to disperse the A prepared material, and it was easy to form a hard lump, which was difficult to disperse in the subsequent shearing. . The impact is that the dispersion of nano-inorganic powder, inorganic fiber and plant fiber is poor, and it is affected in improving the abrasion resistance and reinforcement of polypropylene.

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Abstract

本发明属于塑料功能化技术领域，具体公开了一种耐磨耐老化家具塑料颗粒及制备方法。通过使纳米无机粉体、无机纤维、植物纤维预先分散在液状的石蜡，并在聚丙烯完全熔融的第二加料口加入，以增加分散性，提高塑料的耐磨性。利用POE良好的耐老化性和延展特性，通过预先与抗氧剂、紫外线吸收剂构成复合防老化剂，在用于聚丙烯混炼时，POE的弹性和延展性使得抗氧剂、紫外线吸收剂在混炼物中与聚丙烯均匀分散形成防护，相比于直接将抗氧剂、紫外线吸收剂加入聚丙烯分散的分散效果更好。本发明通过原料的合理组合、预处理、加入方式的改进，使得到的塑料颗粒用于家具具有良好耐磨、耐老化，可以直接通过注塑制备家具或挤出成板材制备家具。

Description

一种耐磨耐老化家具塑料颗粒及制备方法 技术领域
本发明属于塑料功能化技术领域，涉及用于家具的塑料，进一步涉及一种耐磨耐老化家具塑料颗粒及制备方法。
背景技术
传统的，家具主要是采用木材加工而成，而随着建筑装饰业的发展，对木材的需求快速发展。木材由于生长周期长，难以满足巨大的家居需求，各种人造板、胶合木等替原生木材用于家具。然而，带来的环保健康问题也随之产生。
塑料作为目前生产、生活、工业用品的大宗原料，不但涉及领域广泛，而且种类繁多，尤其是随着高分子塑料功能性的不断提升，其在代替金属、木材方面发挥了巨大的作用。因此将塑料用于家具生产得到了快速的发展。塑料家具相对于传统实木家具、藤艺家具、铁艺家具等，是一种新性能的家具，它以色彩鲜艳、形状各异、轻便小巧、适用面广、保养方便变广大消费者所喜欢。
塑料具有重量轻、化学性质稳定、不会锈蚀、耐冲击性好、具有较好的透明性、绝缘性好、着色性好和加工成本较低等优点，用于制作家具可以很好地进行成型，从而减少木质家具使用大量粘接剂，在环保方面具有突出的贡献。塑料家具比起木材或金属材料制成的家具，可塑性极强，可以加工成任何形状，同时它色彩丰富，与其他家具巧妙搭配，可以起到美化居室的作用。
随着技术的发展，目前的塑料家具由最初的简易塑料桌椅向塑料柜子、塑料床等家具。工程塑料具有优良的综合性能，刚性大，蠕变小，机械强度高，耐热性好，电绝缘性好，可在较苛刻的物理环境中长期使用，达到以塑代木的目的。但工程塑料成本高，大件加工性困难。因此，将普通塑料用于家具是目 前众多家具生产企业的选择。
然而，普通的通用塑料聚乙烯(PE)、聚丙烯(PP)、聚氯乙烯(PVC)、聚苯乙烯(PS)，直接制备家具还存在较多问题，主要表现在：1、强度问题，塑料为高分子材料，与纤维质的木材相比强度较低，因此需要合理的改进强度才可以将塑料用于家具；2、耐磨性问题，高分子塑料表现为柔性，耐磨性较差，容易刮花；需要改进其耐磨性和刚性；3、耐老化问题，高分子塑料为高分子量特性，材质会随这光照等缓慢降解老化、褪色，其机械强度不断减小，因此为了延长使用寿命需要解决老化问题。
中国发明专利CN107523007A公开了一种性能优异的耐磨塑料复合板，属于塑料制品技术领域。包括以下重量份的各组份制备而成：聚甲醛塑料40～60份、丙烯腈一丁二烯一苯乙烯共聚合物20～30份、聚甲基丙烯酸酯15～30份、聚乳酸5～10份、抗氧化剂1～5份、耐磨剂5～8份、填充剂10～18份、耐老化剂1～5份、润滑剂1～3份、耐蚀树脂2～5份、碳化硅晶粒5～8份。本发明制得的塑料板耐磨性能优异，机械强度高，耐腐蚀性强，耐高温，抗氧化性能和耐气候性能得到提高，使用寿命大大增加，具有广阔的市场空间。
中国发明专利CN111019311A公开了一种耐磨工程塑料及其制备方法，由以下重量份的材料组成：不饱和聚酯65～75份、聚对苯二甲酸乙二醇酯60～80份、半芳香族尼龙PA6T15～35份、聚四氟乙烯10～12份、钛酸钾晶须增强体10～20份、硫醇丁基锡稳定剂3～5份、添加剂1～5份、偶联剂0.6～1.8份、抗氧剂0.2～0.5份和润滑剂0.7～2.5份，润滑剂为液体石蜡、聚乙烯蜡和单硬脂酸甘油酯中的一种或者多种组合物，本发明涉及工程塑料产品技术领域，该耐磨工程塑料及其制备方法中的各项原料配料合理，并且制成的工程塑料耐磨 的效果显著、持久，力学性能优良，与聚四氟乙烯涂层配合使用的效果更好，在制成工程零件后，自身的损耗较小，在复杂的工作环境下性能变化较小。
现有技术为了获得良好耐磨性的塑料，主要是采用工程塑料，且采用较昂贵的材料进行耐磨改性，尽管耐磨性提升，但成本高，只能在附加值高的产品应用。对于大宗的家具产品，生产企业仍然使用成本较低且易于加工的聚丙烯等普通聚合物。
发明内容
为了实现普通塑料聚丙烯制备的家具具有良好的耐磨性和耐老化性，本发明致在开发一种具有耐磨、耐老化特性的塑料颗粒，该塑料颗粒可以直接用于各种注塑成型、挤出板材等加工，用于塑料家具。
首先，本发明提供一种耐磨耐老化家具塑料颗粒的制备方法，其特征在于：具体制备方法如下：
(1)将纳米无机粉体、硅酮粉进行研磨分散，然后与石蜡以重量比1∶5-8混合，加热至石蜡完全熔化，并高速搅拌，形成纳米粒子预分散液；
(2)将无机纤维、植物纤维粉加入纳米粒子预分散液进一步搅拌分散均匀，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
(3)将POE、抗氧剂、紫外线吸收剂混合加入单螺杆挤出机挤出造粒，得到复合防老化剂，然后送入料仓B；其中，POE、抗氧剂、紫外线吸收剂按照重量份计为：POE 80-90重量份、抗氧剂3-5重量份、紫外线吸收剂2-5重量份。
(4)将聚丙烯、相容剂、偶联剂、填料、色粉，加入高速混合机，在100-120℃高速搅拌均匀，经管道送入料仓C；其中，聚丙烯、相容剂、偶联剂、填料、色粉按照重量份称量：聚丙烯70-80重量份、相容剂1-2重量份、偶联剂0.1-0.2 重量份、填料3-5重量份、色粉0-1重量份。
(5)将料仓B和料仓C的物料通过自动称量以质量比1∶8-10混合，随即经自动提升机送入螺杆挤出机的第一加料；料仓A的物料加入螺杆挤出机的第二加料口；螺杆挤出机的温度设置为：第一段160-180℃、第二段190-200℃、第三段210-220℃、第四段230-225℃、第五段160-180℃；第一加料口设在第一段，第二加料口设在第三段和第四段间，第一加料口与第二加料口的距离控制在65-85cm；经螺杆挤出机挤出，风冷切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
纳米无机粉体用于高分子塑料具有一定的增强作用，同时纳米无机粉体也会增加塑料的耐磨性，然而，如果不能有效的分散，纳米无机粉体在塑料中的界面增强效果和耐磨效果会受到限制。纳米无机粉体如何有效地在塑料中均匀分散是困扰技术人员的一大难题。由于塑料的加工过程是热塑性的粘弹态，显然，纳米无机粉体直接在其中分散是困难的。液态时，纳米无机粉体的分散效果是良好的，为此，本发明将纳米无机粉体与硅酮研磨分散后，与石蜡以重量比1∶5-8，形成的是液态，在液态时高速搅拌，有利于纳米无机粉体的分散。
作为优选，步骤(1)中所述纳米无机粉体、硅酮的质量比为100∶0.5-1；通过硅酮粉研磨分散，一方面使纳米无机粉体团聚的大颗粒解聚分散开，另一方面是纳米无机粉体具有亲油性，易于在熔化的石蜡中分散；再者硅酮粉有利于提高耐磨性及耐擦刮性。纳米无机粉体与硅酮研磨分散后，与石蜡以重量比1∶5-8，使用了较多的石蜡，形成的是液态，在液态时高速搅拌，有利于纳米无机粉体的分散。
作为优选，步骤(1)中所述纳米无机粉体选用纳米碳酸钙、纳米沉淀硫酸 钡、纳米云母粉、纳米蒙脱土、纳米滑石粉、纳米硅藻土、纳米高岭土中的一种或多种的组合。
进一步的，步骤(1)中所述的研磨分散采用成熟的球磨、气流磨均可以达到效果。
进一步的，步骤(1)中所述的加热至石蜡完全熔化，采用的温度使石蜡熔化为准，温度不易过高，过高的温度会导致石蜡挥发和变质；在具体使用时，如选用58#石蜡，可以在70℃的油浴恒温搅拌釜中加热。
进一步的，步骤(1)中所述的高速搅拌，采用800-1000rpm的搅拌速度搅拌20-30min。
作为优选，步骤(2)中所述无机纤维的加入量为纳米粒子预分散液质量的15-20％；植物纤维粉加入量为纳米粒子预分散液质量的15-20％。无机纤维、植物纤维粉不但可以增加塑料的冲击强度，而且可以增加塑料的耐磨性，防止制备的塑料家具刮花；同样的，无机纤维、植物纤维粉在粘弹性的塑料中难以直接分散，本发明预先在液态状的纳米粒子预分散液中分散无机纤维、植物纤维粉，目的是使其在螺杆挤出中易于分散在粘弹性的塑料中。
进一步的，步骤(2)中所述的无机纤维优选玻璃纤维、硅酸铝纤维、硅灰石纤维、水镁石纤维、海泡石纤维、碳酸钙晶须、硫酸钙晶须中的至少一种。
进一步的，步骤(2)中所述的植物纤维粉为过50目筛网的玉米秸秆、小麦秸秆、亚麻秸秆中的一种。更进一步，我们通过大量实验发现，亚麻秸秆粉的加入在提升塑料耐磨性方面效果更为显著。植物纤维粉的加入，使得得到的塑料颗粒制备的家具具有一定的木质感。
作为优选，步骤(3)中将POE、抗氧剂、紫外线吸收剂造粒预先制备复合 防老化剂，POE具有里良好的耐老化性，通过预先与抗氧剂、紫外线吸收剂构成复合防老化剂，在与聚丙烯混炼时，POE的弹性和延展性较好，从而使得抗氧剂、紫外线吸收剂在混炼物中与聚丙烯相间形成防护，促进防老效果。
进一步的，步骤(3)所述抗氧剂选用1010、DLTP、BHT中的一种；所述紫外线吸收剂选用UV-531。
进一步的，步骤(4)所述聚丙烯选用牌号为EPF30R、EPR30R、EPS30R中的至少一种；所述相容剂选用聚丙烯接枝马来酸酐；所述偶联剂选用钛酸酯偶联剂、铝酸酯偶联剂中的一种；所述填料选用玻璃微珠、蛇纹石粉中的一种；其一方面可以辅助塑料的加工流动性，另一方面可以辅助提升塑料的耐磨性和光泽；所述色粉根据具体的颜色需要进行选择，可以是颜料，也可以是市售的色母料；本发明推荐白色选择二氧化钛、珠光色选择云母钛珠光颜料、铁红、铁橙、铁黄、锌铁黄等，不推荐使用含有重金属的颜料如铬绿、铬黄、中铬黄、钼铬红、镉黄、镉橙、镉红等。
作为优选，步骤(5)中所述第二加料口加入的物料是第一加料口加入物料质量的15-20％。通过将料仓B和料仓C的物料加入第一加料口熔融混炼，在第二加料口熔融混炼的物料与预先分散的预备料混炼，预备料易于熔化分散，快速分散在熔融的混炼料中。如果将料仓A、B、C中的物料同时混合后在第一加料口加入，由于聚丙烯混炼熔融具有一定的熔程，起初粘度过大，难以使A预备料分散，易形成硬团，在后续的剪切中分散困难。为此，本发明首先在第一加料口将B、C料仓的物料加入熔融混炼，在完全熔融的第二加料口加入预分散料A，从而促进预分散料A良好的分散。进一步优选的，第一加料口与第二加料口的距离控制在80cm。
作为优选，步骤(5)中所述螺杆挤出机选用同向双螺杆挤出机，同向双螺杆挤出机的剪切分散效果较好，作为优选，利于纳米无机物的分散。进一步优选的，所述螺杆挤出机控制转速为150-200rpm，切粒采用风冷模面切粒。
另外，本发明提供由上述方法制备得到的一种耐磨耐老化家具塑料颗粒。聚丙烯作为目前用于家具的主流塑料，其成本低、易于通过注塑、挤出等工艺加工成大件家具或家具板材，但相比于工程塑料，聚丙烯在用于家具时存在刚性较低、强度较低，制备成的家具不耐磨，易被刮花，而且老化现象明显。因此，本发明针对塑料家具的需要综合改性了聚丙烯，对标国家标准《塑料家具通用技术条件》(GB/T3487-2016)提升聚丙烯的耐磨性和耐老化性。
本发明通过预先将纳米无机粉体与硅酮研磨分散，分散在熔化的石蜡形成液状，通过液状分散使纳米无机粉体得到分散；同时将难以分散的无机纤维、植物纤维预先分散在液状的石蜡液中，以此克服了直接在粘弹态的塑料中不易分散的问题，从而通过纳米无机粉体、无机纤维、植物纤维的充分分散使塑料的耐磨性、强度得到提升。利用POE具有良好的耐老化性，通过预先与抗氧剂、紫外线吸收剂构成复合防老化剂，在与聚丙烯混炼时，POE的弹性和延展性较好，从而使得抗氧剂、紫外线吸收剂在混炼物中与聚丙烯均匀分散形成防护，促进防老效果。通过在第一加料口将B、C料仓的物料加入熔融混炼，在完全熔融的第二加料口加入预分散料A，从而促进预分散料A良好的分散。
有益的效果：
1、本发明为了提升聚丙烯的耐磨性，使纳米无机粉体、无机纤维、植物纤维预先分散的液状的石蜡，并在聚丙烯完全熔融的第二加料口加入，以增加分散性，提高塑料的耐磨性。
2、本发明利用POE良好的耐老化性和延展特性，通过预先与抗氧剂、紫外线吸收剂构成复合防老化剂，在用于聚丙烯混炼时，POE的弹性和延展性使得抗氧剂、紫外线吸收剂在混炼物中与聚丙烯均匀分散形成防护，相比于直接将抗氧剂、紫外线吸收剂加入聚丙烯分散的分散效果更好。
3、本发明通过原料的合理选择、预处理、加入方式的改进，使得到的塑料颗粒用于家具不但具有良好的抗冲击性，而且耐磨、耐老化，可以直接通过注塑制备家具或挤出成板材制备家具。
具体实施方式
为了使本技术领域的人员更好地理解本发明方案，下面将结合实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分的实施例，而不是全部的实施例。基于本发明的技术思路，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
实施例1
(1)将纳米碳酸钙与硅酮粉以质量比100∶1加入球磨机球磨15min，硅酮粉使纳米碳酸钙疏水并分散；然后与58#石蜡以重量比1∶5-8混合，在70℃的油浴恒温搅拌釜中加热至石蜡完全熔化，并采用1000rpm的搅拌速度高速搅拌20min，形成纳米粒子预分散液；
(2)将玻璃纤维、过50目筛网的亚麻秸秆粉加入纳米粒子预分散液进一步搅拌分散均匀，玻璃纤维的加入量为纳米粒子预分散液质量的20％；亚麻秸秆粉加入量为纳米粒子预分散液质量的20％，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
(3)将80重量份POE、3重量份抗氧剂1010、2重量份紫外线吸收剂UV-531混合加入单螺杆挤出机在120℃挤出造粒，得到复合防老化剂，然后送入料仓B；
(4)将70重量份聚丙烯EPF30R、2重量份相容剂聚丙烯接枝马来酸酐、0.2重量份铝酸酯偶联剂、钛酸酯、3重量份玻璃微珠填料、0.3重量份云母钛珠光颜料，加入高速混合机，在100℃高速搅拌均匀，经管道送入料仓C；
(5)将料仓B和料仓C的物料通过自动称量以质量比1∶8混合，随即经自动提升机送入同向双螺杆挤出机的第一加料；料仓A的物料加入螺杆挤出机的第二加料口；第二加料口加入的物料是第一加料口加入物料质量的20％螺杆挤出机的温度设置为：第一段160℃、第二段190℃、第三段210℃、第四段225℃、第五段180℃；第一加料口设在第一段，第二加料口设在第三段和第四段间，第一加料口与第二加料口的距离控制在80cm；控制螺杆转速为150rpm；经同向双螺杆挤出机挤出，风冷模面切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
对比例1
(1)将纳米碳酸钙与硅酮粉以质量比100∶1加入球磨机球磨15min，硅酮粉使纳米碳酸钙疏水并分散；然后与58#石蜡以重量比1∶0.5混合，在70℃的油浴恒温搅拌釜中加热至石蜡完全熔化，并采用1000rpm的搅拌速度高速搅拌20min，形成纳米粒子分散料；
(2)将玻璃纤维、过50目筛网的亚麻秸秆粉加入纳米粒子分散料进一步搅拌分散均匀，玻璃纤维的加入量为纳米粒子预分散料质量的20％；亚麻秸秆粉加入量为纳米粒子预分散料质量的20％，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
(3)将80重量份POE、3重量份抗氧剂1010、2重量份紫外线吸收剂UV-531混合加入单螺杆挤出机在120℃挤出造粒，得到复合防老化剂，然后送入料仓B；
(4)将70重量份聚丙烯EPF30R、2重量份相容剂聚丙烯接枝马来酸酐、0.2重量份铝酸酯偶联剂、钛酸酯、3重量份玻璃微珠填料、0.3重量份云母钛珠光颜料，加入高速混合机，在100℃高速搅拌均匀，经管道送入料仓C；
(5)将料仓B和料仓C的物料通过自动称量以质量比1∶8混合，随即经自动提升机送入同向双螺杆挤出机的第一加料；料仓A的物料加入螺杆挤出机的第二加料口；第二加料口加入的物料是第一加料口加入物料质量的20％；螺杆挤出机的温度设置为：第一段160℃、第二段190℃、第三段210℃、第四段225℃、第五段180℃；第一加料口设在第一段，第二加料口设在第三段和第四段间，第一加料口与第二加料口的距离控制在80cm；控制螺杆转速为150rpm；经同向双螺杆挤出机挤出，风冷模面切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
实施例2
(1)将纳米沉淀硫酸钡与硅酮粉以质量比100∶0.5加入球磨机球磨15min，硅酮粉使纳米沉淀硫酸钡疏水并分散；然后与58#石蜡以重量比1∶6混合，在70℃的油浴恒温搅拌釜中加热至石蜡完全熔化，并采用800rpm的搅拌速度高速搅拌25min，形成纳米粒子预分散液；
(2)将玻璃纤维、过50目筛网的亚麻秸秆粉加入纳米粒子预分散液进一步搅拌分散均匀，玻璃纤维的加入量为纳米粒子预分散液质量的15％；亚麻秸秆粉加入量为纳米粒子预分散液质量的20％，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
(3)将80重量份POE、4重量份抗氧剂DLTP、2重量份紫外线吸收剂UV-531 混合加入单螺杆挤出机在120℃挤出造粒，得到复合防老化剂，然后送入料仓B；
(4)将70重量份聚丙烯EPR30R、2重量份相容剂聚丙烯接枝马来酸酐、0.2重量份偶联剂铝酸酯、3重量份蛇纹石粉填料、0.2重量份锌铁黄颜料，加入高速混合机，在120℃高速搅拌均匀，经管道送入料仓C；
(5)将料仓B和料仓C的物料通过自动称量以质量比1∶10混合，随即经自动提升机送入同向双螺杆挤出机的第一加料；料仓A的物料加入螺杆挤出机的第二加料口；第二加料口加入的物料是第一加料口加入物料质量的18％；螺杆挤出机的温度设置为：第一段160℃、第二段200℃、第三段210℃、第四段225℃、第五段180℃；第一加料口设在第一段，第二加料口设在第三段和第四段间，第一加料口与第二加料口的距离控制在80cm；控制转速为150rpm；经同向双螺杆挤出机挤出，风冷模面切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
对比例2
(1)将纳米沉淀硫酸钡与58#石蜡以重量比1∶6混合，在70℃的油浴恒温搅拌釜中加热至石蜡完全熔化，并采用800rpm的搅拌速度高速搅拌25min，形成纳米粒子预分散液；
(2)将玻璃纤维、过50目筛网的亚麻秸秆粉加入纳米粒子预分散液进一步搅拌分散均匀，玻璃纤维的加入量为纳米粒子预分散液质量的15％；亚麻秸秆粉加入量为纳米粒子预分散液质量的20％，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
(3)将80重量份POE、4重量份抗氧剂DLTP、2重量份紫外线吸收剂UV-531 混合加入单螺杆挤出机在120℃挤出造粒，得到复合防老化剂，然后送入料仓B；
(4)将70重量份聚丙烯EPR30R、2重量份相容剂聚丙烯接枝马来酸酐、0.2重量份偶联剂铝酸酯、3重量份蛇纹石粉填料、0.2重量份锌铁黄颜料，加入高速混合机，在120℃高速搅拌均匀，经管道送入料仓C；
(5)将料仓B和料仓C的物料通过自动称量以质量比1∶10混合，随即经自动提升机送入同向双螺杆挤出机的第一加料；料仓A的物料加入螺杆挤出机的第二加料口；第二加料口加入的物料是第一加料口加入物料质量的18％；螺杆挤出机的温度设置为：第一段160℃、第二段200℃、第三段210℃、第四段225℃、第五段180℃；第一加料口设在第一段，第二加料口设在第三段和第四段间，第一加料口与第二加料口的距离控制在80cm；控制转速为150rpm；经同向双螺杆挤出机挤出，风冷模面切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
实施例3
(1)将纳米滑石粉与硅酮粉以质量比100∶1加入球磨机球磨15min，硅酮粉使纳米滑石粉疏水并分散；然后与58#石蜡以重量比1∶8混合，在70℃的油浴恒温搅拌釜中加热至石蜡完全熔化，并采用1000rpm的搅拌速度高速搅拌20min，形成纳米粒子预分散液；
(2)将海泡石纤维、过50目筛网的玉米秸秆粉加入纳米粒子预分散液进一步搅拌分散均匀，海泡石纤维的加入量为纳米粒子预分散液质量的15％；玉米秸秆粉加入量为纳米粒子预分散液质量的20％，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
(3)将85重量份POE、5重量份抗氧剂BHT、2重量份紫外线吸收剂UV-531 混合加入单螺杆挤出机在120℃挤出造粒，得到复合防老化剂，然后送入料仓B；
(4)将75重量份聚丙烯EPS30R、2重量份相容剂聚丙烯接枝马来酸酐、0.2重量份偶联剂钛酸酯、3重量份玻璃微珠填料、0.2重量份铁橙，加入高速混合机，在100℃高速搅拌均匀，经管道送入料仓C；
(5)将料仓B和料仓C的物料通过自动称量以质量比1∶8混合，随即经自动提升机送入同向双螺杆挤出机的第一加料；料仓A的物料加入螺杆挤出机的第二加料口；第二加料口加入的物料是第一加料口加入物料质量的16％；螺杆挤出机的温度设置为：第一段180℃、第二段200℃、第三段210℃、第四段225℃、第五段170℃；第一加料口设在第一段，第二加料口设在第三段和第四段间，第一加料口与第二加料口的距离控制在80cm；控制转速为200rpm；经同向双螺杆挤出机挤出，风冷模面切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
对比例3
(1)将纳米滑石粉与硅酮粉以质量比100∶1加入球磨机球磨15min，硅酮粉使纳米滑石粉疏水并分散；然后与58#石蜡以重量比1∶8混合，在70℃的油浴恒温搅拌釜中加热至石蜡完全熔化，并采用1000rpm的搅拌速度高速搅拌20min，形成纳米粒子预分散液；
(2)将海泡石纤维、过50目筛网的玉米秸秆粉加入纳米粒子预分散液进一步搅拌分散均匀，海泡石纤维的加入量为纳米粒子预分散液质量的15％；玉米秸秆粉加入量为纳米粒子预分散液质量的20％，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
(3)将85重量份POE、5重量份抗氧剂BHT、2重量份紫外线吸收剂UV-531 混合得到复合防老化剂，然后送入料仓B；
(4)将75重量份聚丙烯EPS30R、2重量份相容剂聚丙烯接枝马来酸酐、0.2重量份偶联剂钛酸酯、3重量份玻璃微珠填料、0.2重量份铁橙，加入高速混合机，在100℃高速搅拌均匀，经管道送入料仓C；
(5)将料仓B和料仓C的物料通过自动称量以质量比1∶8混合，随即经自动提升机送入同向双螺杆挤出机的第一加料；料仓A的物料加入螺杆挤出机的第二加料口；第二加料口加入的物料是第一加料口加入物料质量的16％；螺杆挤出机的温度设置为：第一段180℃、第二段200℃、第三段210℃、第四段225℃、第五段170℃；第一加料口设在第一段，第二加料口设在第三段和第四段间，第一加料口与第二加料口的距离控制在80cm；控制转速为200rpm；经同向双螺杆挤出机挤出，风冷模面切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
实施例4
(1)将纳米滑石粉与硅酮粉以质量比100∶1加入球磨机球磨15min，硅酮粉使纳米滑石粉疏水并分散；然后与58#石蜡以重量比1∶8混合，在70℃的油浴恒温搅拌釜中加热至石蜡完全熔化，并采用1000rpm的搅拌速度高速搅拌20min，形成纳米粒子预分散液；
(2)将玻璃纤维、过50目筛网的亚麻秸秆粉加入纳米粒子预分散液进一步搅拌分散均匀，玻璃纤维的加入量为纳米粒子预分散液质量的15％；亚麻秸秆粉加入量为纳米粒子预分散液质量的15％，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
(3)将85重量份POE、5重量份抗氧剂BHT、2重量份紫外线吸收剂UV-531 混合加入单螺杆挤出机在120℃挤出造粒，得到复合防老化剂，然后送入料仓B；
(4)将75重量份聚丙烯EPS30R、2重量份相容剂聚丙烯接枝马来酸酐、0.2重量份偶联剂钛酸酯、3重量份玻璃微珠填料、0.4重量份铁红，加入高速混合机，在100℃高速搅拌均匀，经管道送入料仓C；
(5)将料仓B和料仓C的物料通过自动称量以质量比1∶8混合，随即经自动提升机送入同向双螺杆挤出机的第一加料；料仓A的物料加入螺杆挤出机的第二加料口；第二加料口加入的物料是第一加料口加入物料质量的20％；螺杆挤出机的温度设置为：第一段180℃、第二段200℃、第三段210℃、第四段225℃、第五段170℃；第一加料口设在第一段，第二加料口设在第三段和第四段间，第一加料口与第二加料口的距离控制在80cm；控制转速为200rpm；经同向双螺杆挤出机挤出，风冷模面切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
对比例4
(1)将纳米滑石粉与硅酮粉以质量比100∶1加入球磨机球磨15min，硅酮粉使纳米滑石粉疏水并分散；然后与58#石蜡以重量比1∶8混合，在70℃的油浴恒温搅拌釜中加热至石蜡完全熔化，并采用1000rpm的搅拌速度高速搅拌20min，形成纳米粒子预分散液；
(2)将玻璃纤维、过50目筛网的亚麻秸秆粉加入纳米粒子预分散液进一步搅拌分散均匀，玻璃纤维的加入量为纳米粒子预分散液质量的15％；亚麻秸秆粉加入量为纳米粒子预分散液质量的15％，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
(3)将85重量份POE、5重量份抗氧剂BHT、2重量份紫外线吸收剂UV-531 混合加入单螺杆挤出机在120℃挤出造粒，得到复合防老化剂，然后送入料仓B；
(4)将75重量份聚丙烯EPS30R、2重量份相容剂聚丙烯接枝马来酸酐、0.2重量份偶联剂钛酸酯、3重量份玻璃微珠填料、0.4重量份铁红，加入高速混合机，在100℃高速搅拌均匀，经管道送入料仓C；
(5)将料仓B和料仓C的物料通过自动称量以质量比1∶8混合，加入料仓A预备料混合均匀，料仓A的物料加入量是B仓料、C物料质量总和的20％；然后将混合料送入螺杆挤出机的第一加料口一次加入，螺杆挤出机的温度设置为：第一段180℃、第二段200℃、第三段210℃、第四段225℃、第五段170℃；控制转速为200rpm；经同向双螺杆挤出机挤出，风冷模面切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
耐老化性测试：
将实施例1-4、对比例1-4得到的塑料颗粒注塑为厚度为4mm的板材，然后裁切为宽10mm，长为80mm的样品进行冲击强度的测试，按照GB/T1043.1-2008(塑料简支梁冲击性能的测定第1部分)进行测试；进一步，将得到的厚度为4mm的板材进行氙气灯光暴照进行老化处理，参照GB/T16422.2-2014(塑料实验室光源暴露试验方法)，为了模拟日光，采用滤光器对氙气弧灯进行过滤，按照方法A循环序号1进行暴露循环，照射500h后测试冲击强度，通过冲击强度光照前后的变化评价耐老化性。氙气弧灯照射样品前后的冲击强度如表1所示。
耐磨性能评价：
将实施例1-4、对比例1-4得到的塑料颗粒注塑为表面光滑的厚度为4mm的板材，参考GB/T 6739-2006(色漆和清漆铅笔法测定漆膜硬度)，利用不同 硬度的铅笔由3B开始刮塑料板表面，逐步提高铅笔硬度，直至刮出划痕，以此衡量板材的耐磨性和耐刮擦性。如表1所示。
表1：
Figure PCTCN2021083284-appb-000001
通过测试，本发明得到的塑料颗粒具有优异的耐老化性，氙气灯光照500h后冲击强度保留大于85％，超过GB/T3487-2016(塑料家具通用技术条件)规定的轻度保留率大于60％，满足家具生产需要。根据适用原则，利用不同硬度的铅笔进行划痕测试，本发明塑料制备的制品硬度高，耐刮擦，具有良好的耐磨性。
对比例1在分散纳米无机粉体时缩减了石蜡的用量，由于石蜡用量的减少，纳米无机粉体不在液状下分散，其分散受到影响，在本发明中表现为纳米粒子未能建立有效的界面耐磨性，同时其纳米增强功能也大幅降低。
对比例2没有加入硅酮粉处理纳米沉淀硫酸钡，对硫酸钡的分散性和与聚丙烯的相容性有一定的影响，而且硅酮粉用于塑料具有耐刮擦性，因而对聚丙 烯的耐磨性有一定的影响。
对比例3中POE、抗氧剂BHT、紫外线吸收剂UV-531没有利用螺杆熔融混炼分散，而是直接以粉末混合备用，从而使得抗氧剂、紫外线吸收剂在与聚丙烯混炼均匀性变差，影响紫外线吸收剂对紫外光的吸收，影响耐老化性。
对比例4没有将A料在第二加料口加入，即没有在聚丙烯完全熔融态下加入，起初粘度过大，难以使A预备料分散，易形成硬团，在后续的剪切中分散困难。造成的影响是纳米无机粉体、无机纤维、植物纤维的分散较差，在改进聚丙烯耐磨性方面、增强方面受到影响。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。

Claims (10)

  1. 一种耐磨耐老化家具塑料颗粒的制备方法，其特征在于：具体制备方法如下：
    (1)将纳米无机粉体、硅酮粉进行研磨分散，然后与石蜡以重量比1∶5-8混合，加热至石蜡完全熔化，并高速搅拌，形成纳米粒子预分散液；
    (2)将无机纤维、植物纤维粉加入纳米粒子预分散液进一步搅拌分散均匀，冷却后粉碎为细小颗粒，作为预备料存储在料仓A；
    (3)将POE、抗氧剂、紫外线吸收剂混合加入单螺杆挤出机挤出造粒，得到复合防老化剂，然后送入料仓B；其中，POE、抗氧剂、紫外线吸收剂按照重量份计为：POE 80-90重量份、抗氧剂3-5重量份、紫外线吸收剂2-5重量份。
    (4)将聚丙烯、相容剂、偶联剂、填料、色粉，加入高速混合机，在100-120℃高速搅拌均匀，经管道送入料仓C；其中，聚丙烯、相容剂、偶联剂、填料、色粉按照重量份称量：聚丙烯70-80重量份、相容剂1-2重量份、偶联剂0.1-0.2重量份、填料3-5重量份、色粉0-1重量份。
    (5)将料仓B和料仓C的物料通过自动称量以质量比1∶8-10混合，随即经自动提升机送入螺杆挤出机的第一加料；料仓A的物料加入螺杆挤出机的第二加料口；螺杆挤出机的温度设置为：第一段160-180℃、第二段190-200℃、第三段210-220℃、第四段230-225℃、第五段160-180℃；第一加料口设在第一段，第二加料口设在第三段和第四段间，第一加料口与第二加料口的距离控制在65-85cm；经螺杆挤出机挤出，风冷切粒，振动筛分，包装，得到一种耐磨耐老化家具塑料颗粒。
  2. 根据权利要求1所述一种耐磨耐老化家具塑料颗粒的制备方法，其特 征在于：步骤(1)中所述纳米无机粉体、硅酮的质量比为100∶0.5-1。
  3. 根据权利要求1所述一种耐磨耐老化家具塑料颗粒的制备方法，其特征在于：步骤(1)中所述纳米无机粉体选用纳米碳酸钙、纳米沉淀硫酸钡、纳米云母粉、纳米蒙脱土、纳米滑石粉、纳米硅藻土、纳米高岭土中的一种或多种的组合。
  4. 根据权利要求1所述一种耐磨耐老化家具塑料颗粒的制备方法，其特征在于：步骤(1)中所述的高速搅拌，采用800-1000rpm的搅拌速度搅拌20-30min。
  5. 根据权利要求1所述一种耐磨耐老化家具塑料颗粒的制备方法，其特征在于：步骤(2)中所述无机纤维的加入量为纳米粒子预分散液质量的15-20％；植物纤维粉加入量为纳米粒子预分散液质量的15-20％；其中，所述的无机纤维优选玻璃纤维、硅酸铝纤维、硅灰石纤维、水镁石纤维、海泡石纤维、碳酸钙晶须、硫酸钙晶须中的至少一种；所述的植物纤维粉为过50目筛网的玉米秸秆、小麦秸秆、亚麻秸秆中的一种。
  6. 根据权利要求1所述一种耐磨耐老化家具塑料颗粒的制备方法，其特征在于：步骤(3)中所述抗氧剂选用1010、DLTP、BHT中的一种；所述紫外线吸收剂选用UV-531。
  7. 根据权利要求1所述一种耐磨耐老化家具塑料颗粒的制备方法，其特征在于：步骤(4)中所述聚丙烯选用牌号为EPF30R、EPR30R、EPS30R中的至少一种；所述相容剂选用聚丙烯接枝马来酸酐；所述偶联剂选用钛酸酯偶联剂、铝酸酯偶联剂中的一种；所述填料选用玻璃微珠、蛇纹石粉中的一种。
  8. 根据权利要求1所述一种耐磨耐老化家具塑料颗粒的制备方法，其特 征在于：步骤(5)中所述第二加料口加入的物料是第一加料口加入物料质量的15-20％。
  9. 根据权利要求1所述一种耐磨耐老化家具塑料颗粒的制备方法，其特征在于：步骤(5)中所述螺杆挤出机选用同向双螺杆挤出机，所述螺杆挤出机控制转速为150-200rpm。
  10. 一种耐磨耐老化家具塑料颗粒，其特征是由权利要求1-9任一项所述的方法制备得到。
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