PP material for turnover box

Abstract

The invention belongs to the field of plastics. The invention relates to a PP material for a turnover box and a preparation method of the PP material. The PP material for the turnover box comprises the following raw materials in parts by weight: 50-75 parts of PP; 5 to 25 parts of PE; 4.0 to 6.0 parts of a toughening agent; 1.0 to 2.0 parts of a macromolecular compatibilizer; 2.0 to 4.0 parts of a functional modifier; 15-30 parts of pigment and filler; 0.3 to 1.0 part of an antioxidant; 0.2 to 0.6 part of a light stabilizer; 0.2 to 0.5 part of a lubricant; the components are respectively subjected to processes of filler pretreatment, mixing, extrusion and granulation, and a specific side charging process is utilized to prepare the composite material. The novel PP material for the turnover box effectively solves the problems of poor impact resistance, aging resistance and wear resistance of the PP material for the turnover box in the prior art.

Description

Technical Field

[0001] The invention relates to a PP material for a turnover box and a preparation method thereof. The invention belongs to the field of plastics. Background Art

[0002] At present, most of the crates used in the turnover box industry are wooden crates, but wooden crates need to be sterilized at high temperature before use. After arriving at the destination, wooden crates are generally treated as waste. This situation causes a large number of trees to be cut down during the production of wooden crates, wastes fuel, causes waste pollution, and damages the ecological environment. Therefore, people hope to use reusable and recyclable polymer materials (such as polypropylene, etc.) to produce new turnover boxes.

[0003] At present, the commonly used turnover box materials include PE materials, PP materials, etc. The use of PE materials (mainly HDPE) has high gloss, hardness, strong flexibility, strong impact resistance, and is suitable for loading heavy products, such as for stacking; at the same time, it has outstanding low temperature resistance and still has good toughness at around -40°C; but there is a problem of poor heat resistance. PP materials have good shaping, are not easy to deform, have strong flexibility, strong impact resistance, and are cold and heat resistant. It has good heat resistance (about 20°C higher than HDPE), high rigidity and high strength; but there are also some shortcomings, such as poor outdoor aging resistance, insufficient strength, and poor impact resistance. Therefore, the above materials alone cannot fully meet the actual needs as a packaging material.

[0004] In order to further improve the application of polymer materials in turnover boxes, blending and modification of PE and PP has become the preferred research direction. Taking PP as the main body, modification research is carried out on PP to meet the market demand for high impact resistance and high weather resistance of turnover boxes. Summary of the invention

[0005] The purpose of the present invention is to provide a new type of PP material for turnover boxes and its preparation method in view of the problems of poor impact resistance and poor aging resistance of PP materials for turnover boxes in the prior art. After formula design optimization, compounding with homemade functional modifiers, toughening agents and other additives, and side feeding melt extrusion granulation, the above problems can be effectively solved. The technical solution adopted by the present invention to solve its technical problems is: The present invention provides a PP material for a turnover box, comprising the following raw materials in parts by weight: PP 50-75 copies; PE 5-25 parts; 4.0-6.0 parts of toughening agent; 1.0-2.0 parts of macromolecular compatibilizer; Functional modifier 2.0-4.0 parts; 15-30 parts of pigments and fillers; Antioxidant 0.3-1.0 part; Light stabilizer 0.2-0.6 parts; Lubricant 0.2-0.5 parts; The preparation method of the toughening agent comprises the following steps: S11, surface-modifying calcium carbonate with a silane coupling agent containing a carbon-carbon double bond to obtain an intermediate product; The usage ratio of calcium carbonate to the silane coupling agent containing a carbon-carbon double bond is 1g:3.5-5.5g; S12, mixing and granulating the intermediate product, maleic anhydride, POE and DCP to obtain a target product, i.e., the toughening agent; The usage ratio of the intermediate product, maleic anhydride, POE and DCP is 10g: 0.5-1.5g: 10-20g: 0.05g; as well as The preparation method of the functional modifier comprises the following steps: S21, free radical polymerization of epoxy olefins, versatile vinyl carbonate, hard monomers, and soft monomers to obtain a target product, namely, the functional modifier; The usage ratio of the epoxy olefins, versatile vinyl carbonate, hard monomer and soft monomer is 0.5-1.0g: 4.5-5.5g: 1.0-2.0g: 2.0-3.5g.

[0006] Further, the calcium carbonate particle size is 2000-3000 mesh; and The silane coupling agent containing carbon-carbon double bonds is vinyl silane or acryloxy silane.

[0007] Furthermore, the melt index of the POE is 5-10 g / 10 min.

[0008] Further, the versatile vinyl carbonate is VV10 or VV9; The hard monomer is methyl methacrylate or styrene; and The soft monomer is butyl acrylate, isooctyl acrylate or lauryl acrylate.

[0009] Furthermore, the PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 1.0-2.0:1; and The melt index of the copolymer PP is 60-100 g / 10 min; the melt index of the homopolymer PP is 25-30 g / 10 min.

[0010] Furthermore, the PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:1.0-3.0.

[0011] Furthermore, the macromolecular compatibilizer is PP-g-MAH.

[0012] Furthermore, the pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:2.0-4.0; and The titanium dioxide is rutile titanium dioxide.

[0013] The present invention also provides a method for preparing PP material for turnover box, comprising the following steps: S31, mixing; The PP, macromolecular compatibilizer and functional modifier are mixed evenly to obtain component I; the other raw materials in the formula are mixed evenly to obtain component II; S32, extrusion; Component I in S31 is added from the main feeding port of the extruder, and component II is added from the side feeding port, and melt blended and extruded; S33, granulation; The melt in S32 is subjected to the processes of drawing, cooling and pelletizing to obtain PP material for turnover boxes.

[0014] Further, The extruder has a screw length-to-diameter ratio of 50-60:1 and a rotation speed of 300-400 rpm; and The temperatures of the screw sections of the extruder are 175-185°C in zone 1, 185-195°C in zone 2, 190-200°C in zone 3, 190-200°C in zone 4, 190-200°C in zone 5, 195-205°C in zone 6, 195-205°C in zone 7, 205-215°C in zone 8, 205-215°C in zone 9, 210-220°C in zone 10, 210-220°C in zone 11, and 205-215°C in zone 12; The side feed port is located in the third zone or the fourth zone of the extruder.

[0015] Beneficial effects of the present invention: (1) The present invention provides a PP material for a turnover box, wherein PP and PE constitute a resin system in the formula system, wherein PP is compounded in the form of homopolymer PP and copolymer PP. First, homopolymer PP has high crystallinity, thus having high heat resistance and wear resistance; while the regularity of the molecular chain of copolymer PP decreases, thus having good impact resistance; compounding the two can have both high heat resistance and good impact resistance; second, compounding and blending PP with different melt indexes is conducive to balancing the processability and appearance performance of the product.

[0016] (2) The present invention provides a PP material for a turnover box, wherein PP and PE form a resin system, wherein PE is compounded with HDPE and LLDPE. First, HDPE has a high hardness and can be stacked; while the flexible chain of LLDPE has impact resistance; and also has excellent tensile strength, crack resistance and puncture resistance; second, PE has good compatibility with POE toughening agent, which can effectively improve mechanical properties.

[0017] (3) The present invention provides a PP material for a turnover box, in which a self-made toughening agent is used in the formula system to embed the calcium carbonate structure of POE. On the one hand, the embedding structure is a typical core-shell structure with calcium carbonate as the core layer and POE as the shell layer, which improves the toughening effect of POE; at the same time, it also has the strengthening effect of calcium carbonate; on the other hand, this structure can make the volume of POE relatively increase, which has an amplified synergistic effect.

[0018] (4) The present invention provides a PP material for turnover boxes, in which a self-made functional modifier is used in the formula system, which is a macromolecule having an epoxy group, a tertiary carbonate, and a soft segment and a hard segment structure. First, the epoxy structure can undergo a ring-opening reaction with a macromolecular compatibilizer containing maleic anhydride to form a branched structure with a large molecular weight, which can improve the impact resistance of the product; second, the tertiary carbonate structure has a large alkyl substituent, which produces a large steric hindrance and shielding effect, and has excellent anti-cracking, anti-oxidation and UV resistance properties; third, the combination of the soft and hard segment structure has excellent hardness to improve wear resistance, and also has excellent toughness to improve impact resistance.

[0019] (5) The present invention provides a PP material for a turnover box, wherein the pigment and filler in the formula system are compounded with rutile titanium dioxide and talcum powder. First, rutile titanium dioxide can effectively shield light and has excellent aging resistance; second, talcum powder has a lamellar structure, and relative slip between the lamellar structures can be found when the product is impacted, which has a certain impact resistance and wear resistance; at the same time, the inorganic lamellar structure can have a blocking effect on small molecular structures such as water vapor and free radicals, and synergistically improve the aging resistance.

[0020] (6) The present invention provides a method for preparing PP material for turnover boxes. Through the side feeding melt extrusion process, component I formed by PP and a macromolecular expander and a functional modifier is added from the main feeding port for effective blending and melting, and component II enters the screw through the side feeding port and is sheared, dispersed, melted and extruded by an ultra-long aspect ratio screw; time is reserved for component I to generate a macromolecular branched chain structure through a shear reaction, thereby effectively improving the dispersibility of each component, thereby improving the mechanical properties and the like. DETAILED DESCRIPTION

[0021] The present invention is described in detail below with reference to the examples. However, it should be understood that the following examples are only illustrative of the embodiments of the present invention, and are not intended to limit the scope of the present invention.

[0022] The purpose of the present invention is to develop a high-performance PP material for turnover boxes in view of the problems of poor impact resistance and poor weather resistance of PP materials for turnover boxes in the prior art. The idea of ​​implementation is: take PP as the main body, physically blend with PE to complement each other's advantages, and prepare a resin main body with high heat resistance and stackability. Among them, firstly, PP with different melt indexes are blended to obtain a resin material with excellent mechanical properties and thermal properties; HDPE (high strength) and LLDPE (flexibility) are blended simultaneously; then, in order to improve the impact resistance, POE is added as a toughening agent and small-sized calcium carbonate is used as the core for extrusion processing modification to prepare a modified toughening agent of inorganic core layer and organic shell layer; in order to improve the aging resistance, on the basis of adding inorganic fillers, a self-made functional modifier is compounded, with tert-butyl ethylene carbonate as the main structure, which has large steric hindrance and shielding effect, and has high efficiency weather resistance; at the same time, the added pigment filler also has the functions of strengthening, improving heat deformation temperature and wear resistance. To achieve the above purpose: the present invention uses a homemade toughening agent to graft copolymerize calcium carbonate treated with a silane coupling agent with POE and maleic anhydride by melt extrusion, so that the filler is embedded in the POE structure to form a "core-shell structure", which can exert the maximum toughening effect achieved by limited POE, and has synergistic, toughening and strengthening effects; at the same time, a homemade functional modifier is used, through free radical polymerization reaction with tert-butyl vinyl carbonate and epoxy olefin as main raw materials, and with a side feeding process, it is pretreated with PP-g-MAH and PP, and reacted by melt graft copolymerization; after formula design, suitable fillers (titanium dioxide and talc powder compounded) and other additives are extruded to obtain the target product.

[0023] In the present invention, the homemade toughening agent can improve the impact resistance of the material; the functional modifier and the pigment and filler can synergistically improve the aging resistance of the material, and the functional modifier is a macromolecular branched structure of PP-g-MAH, which has the effect of synergistically improving the impact resistance; the talcum powder in the pigment and filler is a lamellar structure, which can undergo relative slip when subjected to force, and has an auxiliary impact resistance effect; in addition, the pigment and filler also have the functions of increasing thermal deformation temperature and wear resistance. The above-mentioned component raw materials are extruded and granulated with resins, additives, etc. to obtain the target material, which can solve the problems of poor impact resistance and poor weather resistance of PP materials used in turnover boxes. The embodiments of the present invention are as follows: The present invention provides a PP material for a turnover box, comprising the following raw materials in parts by weight: PP 50-75 copies; PE 5-25 parts; 4.0-6.0 parts of toughening agent; 1.0-2.0 parts of macromolecular compatibilizer; Functional modifier 2.0-4.0 parts; 15-30 parts of pigments and fillers; Antioxidant 0.3-1.0 part; Light stabilizer 0.2-0.6 parts; Lubricant 0.2-0.5 parts; The preparation method of the toughening agent comprises the following steps: S11, add calcium carbonate and a silane coupling agent containing a carbon-carbon double bond to ethanol, ultrasonically oscillate for 0.5 h, stand at room temperature for 2 h, react at 40-60° C. for 6-10 h, filter, take out the insoluble matter, rinse with ethanol B three times, and then dry the insoluble matter at 60° C. for 12 h to obtain an intermediate product.

[0024] The usage ratio of the calcium carbonate, the silane coupling agent containing a carbon-carbon double bond, and ethanol is 1g:3.5-5.5g:80mL.

[0025] The calcium carbonate particle size is 2000-3000 mesh.

[0026] The silane coupling agent containing a carbon-carbon double bond may be a vinyl silane coupling agent or an acryloxy silane coupling agent; The vinyl silane coupling agent may be KH151, KH171, KH172 or KH173, etc., and KH171 is preferred.

[0027] The acryloxysilane coupling agent may be KH570, KH571, KH670, GX572, etc., and KH570 is preferred.

[0028] S12, adding the intermediate product, maleic anhydride and DCP to acetone, ultrasonically dispersing for 2 hours, adding to POE, mixing evenly, drying at room temperature, adding the mixture to a twin-screw extruder for mixing and granulation to obtain the target product, i.e., the toughening agent.

[0029] The usage ratio of the intermediate product, maleic anhydride, POE and DCP is 10g: 0.5-1.5g: 10-20g: 0.05g.

[0030] The POE has a melt index of 5-10 g / 10 min and may be ENGAGE 8207 (Dow Chemical) or LC670 (LG, South Korea). In addition, the POE described in the following embodiments of the present invention is ENGAGE 8207.

[0031] The temperatures of the twin-screw extruder are 175° C. in zone 1, 180° C. in zone 2, 185° C. in zone 3, 195° C. in zone 4, and 205° C. in zone 5, respectively; the die is 200° C.; and the screw speed is 200 rpm.

[0032] as well as The preparation method of the functional modifier comprises the following steps: S21, adding epoxy olefins, versatate vinyl carbonate, hard monomer, soft monomer and initiator AIBN to N,N-dimethylformamide, heating to 80-90°C, stirring for 6-10h; after the reaction is completed, distilling under reduced pressure, vacuum drying at 60°C for 6h, to obtain the target product, i.e. the functional modifier.

[0033] The usage ratio of the epoxy olefins, versatile vinyl carbonate, hard monomer, soft monomer, initiator AIBN and N,N-dimethylformamide is 0.5-1.0g:4.5-5.5g:1.0-2.0g:2.0-3.5g:0.2g:100mL.

[0034] The epoxy olefins may be glycidyl methacrylate, (glycidyloxy)ethyl methacrylate, allyl glycidyl ether, 1,2-epoxy-7-octene or 1,2-epoxy-9-decene, etc.; and (glycidyloxy)ethyl methacrylate is preferred.

[0035] The versatile vinyl carbonate is VV10 or VV9; The hard monomer is methyl methacrylate or styrene; and The soft monomer is butyl acrylate, isooctyl acrylate or lauryl acrylate.

[0036] The PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 1.0-2.0:1; and The melt index of the copolymer PP is 60-100g / 10min; when the melt index is less than 60 g / 10min, the molecular weight is large and the processing and molding is difficult; and when the melt index is greater than 100 g / 10min, the molecular weight is small and the mechanical properties are low, thus affecting the product quality; therefore, the copolymer PP can be K7760H (Yanshan Petrochemical), M60T (Zhenhai Refining and Chemical), EPL31UA (Iran JPC), EP640V (South Korea Dalin), etc.; from the perspective of easy access to raw materials, K7760H (Yanshan Petrochemical) is preferred in the embodiments of the present invention, and the copolymer PP described in the following embodiments of the present invention is K7760H. The melt index of the homopolymer PP is 25-30g / 10min; it can be Z30S (Fushun Petrochemical), etc., and the homopolymer PP described in the following embodiments of the present invention is Z30S.

[0037] The PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:1.0-3.0; The HDPE may be 2200J (Yanshan Petrochemical); and the HDPE described in the following embodiments of the present invention is 2200J.

[0038] The LLDPE may be DADF7042 (Guangzhou Maoming Petrochemical Ethylene Industrial Company), ML2502 (Zhongyuan Petrochemical), 7042 (Fushun Petrochemical), 7047 (Daqing Petrochemical), etc., and the LLDPE described in the following embodiments of the present invention is DADF7042.

[0039] The macromolecular compatibilizer is PP-g-MAH, purchased from Jiayirong Polymer (Shanghai) Co., Ltd., model CMG5701, and the grafting rate is 1.03%.

[0040] The pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:2.0-4.0; and The titanium dioxide is rutile titanium dioxide; The talcum powder has a particle size of 1000-3000 mesh; and the particle size of the talcum powder described in the following embodiments of the present invention is 1250 mesh.

[0041] The antioxidant is a mixture of hindered phenols and phosphites in a mass ratio of 1 / 2. In addition, the antioxidant described in the following embodiments of the present invention is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1 / 2.

[0042] The light stabilizer is a mixture of hindered amines and ultraviolet absorbers in a mass ratio of 1 / 2. In addition, the light stabilizer in the following embodiments of the present invention is a mixture of UV-770 and UV-41 in a mass ratio of 1 / 2.

[0043] The lubricant is OPE wax, erucic acid amide, ethylene bisstearamide, etc.; and, the lubricant in the following embodiments of the present invention is ethylene bisstearamide.

[0044] The embodiment of the present invention also provides a method for preparing PP material for a turnover box, comprising the following steps: S31, mixing; PP, macromolecular compatibilizer and functional modifier were added into a mixer, and stirred at a stirring rate of 300 r / min for 30 min to obtain component I; other raw materials in the formula were stirred at a stirring rate of 800 r / min for 10 min to obtain component II; S32, extrusion; Component I in S31 is added from the main feeding port of the extruder, and component II is added from the side feeding port, and melt blended and extruded; The extruder has a screw length-to-diameter ratio of 50-60:1 and a rotation speed of 300-400 rpm; and The temperatures of the screw sections of the extruder are 175-185°C in zone 1, 185-195°C in zone 2, 190-200°C in zone 3, 190-200°C in zone 4, 190-200°C in zone 5, 195-205°C in zone 6, 195-205°C in zone 7, 205-215°C in zone 8, 205-215°C in zone 9, 210-220°C in zone 10, 210-220°C in zone 11, and 205-215°C in zone 12; The side feed port is located in the third zone or the fourth zone of the extruder.

[0045] S33, granulation; The melt in S32 is subjected to the processes of strand drawing, cooling and pelletizing to obtain PP material for turnover boxes.

[0046] In order to further understand the present invention, a PP material for a turnover box provided by the present invention is described in detail below in conjunction with specific embodiments. The protection scope of the present invention is not limited by the following embodiments.

[0047] A PP material for a turnover box, comprising the following raw materials in parts by weight: PP 65 copies; PE 15 copies; 5.0 parts of toughening agent; 1.5 parts of macromolecular compatibilizer; 3.0 parts of functional modifier; 24 parts of pigments and fillers; 0.6 parts of antioxidant; Light stabilizer 0.4 parts; 0.3 parts of lubricant; The preparation method of the toughening agent comprises the following steps: S11, add calcium carbonate and silane coupling agent KH171 to ethanol, ultrasonically oscillate for 0.5 h, let stand at room temperature for 2 h, react at 50°C for 7.5 h, filter, take out the insoluble matter, rinse with ethanol B three times, and then dry the insoluble matter at 60°C for 12 h to obtain an intermediate product.

[0048] The usage ratio of calcium carbonate, silane coupling agent KH171 and ethanol is 1g:4.5g:80mL.

[0049] The calcium carbonate particle size is 2500 meshes.

[0050] Its infrared data are as follows: 1622cm -1 :-C=C- exists; 1383cm -1 :-CO- exists; 1109 cm-1 、798cm -1 :-Si-O- exists; 711cm -1 :-Ca-O- exists.

[0051] S12, adding the intermediate product, maleic anhydride and DCP to acetone, ultrasonically dispersing for 2 hours, adding to POE, mixing evenly, drying at room temperature, adding the mixture to a twin-screw extruder for mixing and granulation to obtain the target product, i.e., the toughening agent.

[0052] The usage ratio of the intermediate product, maleic anhydride, POE and DCP is 10g:1.0g:15g:0.05g.

[0053] The temperatures of the twin-screw extruder are 175° C. in zone 1, 180° C. in zone 2, 185° C. in zone 3, 195° C. in zone 4, and 205° C. in zone 5, respectively; the die is 200° C.; and the screw speed is 200 rpm.

[0054] Its infrared data are as follows: 2904cm -1 :-CC-exists; 1786cm -1 :-C=O (anhydride) exists; 1622cm -1 :-C=C- does not exist; 1383cm -1 :-CO- exists; 1109 cm -1 、798cm -1 :-Si-O- exists; 711cm -1 :-Ca-O- exists.

[0055] as well as The preparation method of the functional modifier comprises the following steps: S21, ethyl methacrylate, tert-butyl vinyl carbonate VV10, methyl methacrylate, isooctyl acrylate, initiator AIBN were added to N,N-dimethylformamide, the temperature was raised to 85°C, and stirred for 8.5h; after the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 60°C for 6h to obtain the target product ( ), that is, the functional modifier.

[0056] The usage ratio of (glycidyloxy)ethyl methacrylate, versatate VV10, methyl methacrylate, isooctyl acrylate, initiator AIBN, and N,N-dimethylformamide is 0.8g:5.0g:1.5g:2.7g:0.2g:100mL.

[0057] Its infrared data are as follows: 1735cm -1 :-C=O exists; 1623cm -1 :-C=C- does not exist; 1605 cm-1 、811cm -1 :-C=C- does not exist; 1262cm -1 、927cm -1 、794cm -1 : Epoxy group exists.

[0058] The PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 1.5:1.

[0059] The PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:2.0.

[0060] The pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:3.0.

[0061] A method for preparing PP material for a turnover box comprises the following steps: S31, mixing; PP, macromolecular compatibilizer and functional modifier were added into a mixer, and stirred at a stirring rate of 300 r / min for 30 min to obtain component I; other raw materials in the formula were stirred at a stirring rate of 800 r / min for 10 min to obtain component II; S32, extrusion; Component I in S31 is added from the main feeding port of the extruder, and component II is added from the side feeding port, and melt blended and extruded; The extruder has a screw length-to-diameter ratio of 56:1 and a screw speed of 362 rpm; and The temperatures of the screw sections of the extruder are 180°C for zone 1, 190°C for zone 2, 193°C for zone 3, 195°C for zone 4, 198°C for zone 5, 200°C for zone 6, 203°C for zone 7, 208°C for zone 8, 211°C for zone 9, 215°C for zone 10, 215°C for zone 11, and 200°C for zone 12; The side feed port is located in the third zone of the extruder.

[0062] S33, granulation; The melt in S32 is subjected to the processes of strand drawing, cooling and pelletizing to obtain PP material for turnover boxes.

[0063] A PP material for a turnover box, comprising the following raw materials in parts by weight: PP 50 copies; PE 25 copies; 4.0 parts of toughening agent; 2.0 parts of macromolecular compatibilizer; Functional modifier 4.0 parts; 15 parts of pigments and fillers; 1.0 part of antioxidant; Light stabilizer 0.2 parts; 0.5 parts of lubricant; The preparation method of the toughening agent comprises the following steps: S11, add calcium carbonate and silane coupling agent KH171 to ethanol, ultrasonically oscillate for 0.5 h, stand at room temperature for 2 h, react at 40°C for 10 h, filter, take out the insoluble matter, rinse with ethanol B three times, and dry the insoluble matter at 60°C for 12 h to obtain an intermediate product.

[0064] The usage ratio of calcium carbonate, silane coupling agent KH171 and ethanol is 1g:5.5g:80mL.

[0065] The calcium carbonate particle size is 2000 mesh.

[0066] Its infrared data are as follows: 1622cm -1 :-C=C- exists; 1383cm -1 :-CO- exists; 1109 cm -1 、798cm -1 :-Si-O- exists; 711cm -1 :-Ca-O- exists.

[0067] S12, adding the intermediate product, maleic anhydride and DCP to acetone, ultrasonically dispersing for 2 hours, adding to POE, mixing evenly, drying at room temperature, adding the mixture to a twin-screw extruder for mixing and granulation to obtain the target product, i.e., the toughening agent.

[0068] The usage ratio of the intermediate product, maleic anhydride, POE and DCP is 10g:1.5g:20g:0.05g.

[0069] The temperatures of the twin-screw extruder are 175° C. in zone 1, 180° C. in zone 2, 185° C. in zone 3, 195° C. in zone 4, and 205° C. in zone 5, respectively; the die is 200° C.; and the screw speed is 200 rpm.

[0070] Its infrared data are as follows: 2904cm -1 :-CC-exists; 1786cm -1 :-C=O (anhydride) exists; 1622cm -1 :-C=C- does not exist; 1383cm -1 :-CO- exists; 1109 cm -1 、798cm -1 :-Si-O- exists; 711cm -1 :-Ca-O- exists.

[0071] as well as The preparation method of the functional modifier comprises the following steps: S21, ethyl methacrylate, tert-butyl carbonate VV10, styrene, butyl acrylate, initiator AIBN were added to N,N-dimethylformamide, the temperature was raised to 80°C, and stirred for 10 hours; after the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 60°C for 6 hours to obtain the target product ( ), that is, the functional modifier.

[0072] The usage ratio of (glycidyloxy)ethyl methacrylate, versatate VV10, styrene, butyl acrylate, initiator AIBN, and N,N-dimethylformamide is 1.0g:4.5g:1.0g:3.5g:0.2g:100mL.

[0073] Its infrared data are as follows: 3011cm -1 、1595cm -1 、1498cm -1 : benzene ring exists; 1735cm -1 :-C=O exists; 1623cm -1 :-C=C- does not exist; 1605 cm -1 、811cm -1 :-C=C- does not exist; 1262cm -1 、927cm -1 、794cm -1 : Epoxy group exists.

[0074] The PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 1.5:1.

[0075] The PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:2.0.

[0076] The pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:3.0.

[0077] A method for preparing PP material for a turnover box comprises the following steps: S31, mixing; PP, macromolecular compatibilizer and functional modifier were added into a mixer, and stirred at a stirring rate of 300 r / min for 30 min to obtain component I; other raw materials in the formula were stirred at a stirring rate of 800 r / min for 10 min to obtain component II; S32, extrusion; Component I in S31 is added from the main feeding port of the extruder, and component II is added from the side feeding port, and melt blended and extruded; The extruder has a screw length-to-diameter ratio of 50:1 and a screw speed of 394 rpm; and The temperatures of the screw sections of the extruder are 175°C in zone 1, 185°C in zone 2, 190°C in zone 3, 190°C in zone 4, 190°C in zone 5, 195°C in zone 6, 198°C in zone 7, 205°C in zone 8, 207°C in zone 9, 210°C in zone 10, 210°C in zone 11, and 205°C in zone 12; The side feed port is located in the fourth zone of the extruder.

[0078] S33, granulation; The melt in S32 is subjected to the processes of strand drawing, cooling and pelletizing to obtain PP material for turnover boxes.

[0079] A PP material for a turnover box, comprising the following raw materials in parts by weight: PP 75 copies; PE 5 copies; 6.0 parts of toughening agent; 1.0 part of macromolecular compatibilizer; 2.0 parts of functional modifier; 30 parts of pigments and fillers; 0.3 parts of antioxidant; Light stabilizer 0.6 part; 0.2 parts of lubricant; The preparation method of the toughening agent comprises the following steps: S11, add calcium carbonate and silane coupling agent KH171 to ethanol, ultrasonically oscillate for 0.5 h, let stand at room temperature for 2 h, react at 60°C for 6 h, filter, take out the insoluble matter, rinse with ethanol B three times, and then dry the insoluble matter at 60°C for 12 h to obtain an intermediate product.

[0080] The usage ratio of calcium carbonate, silane coupling agent KH171 and ethanol is 1g:3.5g:80mL.

[0081] The calcium carbonate particle size is 3000 mesh.

[0082] Its infrared data are as follows: 1622cm -1 :-C=C- exists; 1383cm -1 :-CO- exists; 1109 cm -1 、798cm -1 :-Si-O- exists; 711cm -1 :-Ca-O- exists.

[0083] S12, adding the intermediate product, maleic anhydride and DCP to acetone, ultrasonically dispersing for 2 hours, adding to POE, mixing evenly, drying at room temperature, adding the mixture to a twin-screw extruder for mixing and granulation to obtain the target product, i.e., the toughening agent.

[0084] The usage ratio of the intermediate product, maleic anhydride, POE and DCP is 10g:0.5g:10g:0.05g.

[0085] The temperatures of the twin-screw extruder are 175° C. in zone 1, 180° C. in zone 2, 185° C. in zone 3, 195° C. in zone 4, and 205° C. in zone 5, respectively; the die is 200° C.; and the screw speed is 200 rpm.

[0086] Its infrared data are as follows: 2904cm -1 :-CC-exists; 1786cm -1 :-C=O (anhydride) exists; 1622cm -1 :-C=C- does not exist; 1383cm -1 :-CO- exists; 1109 cm -1 、798cm -1 :-Si-O- exists; 711cm -1 :-Ca-O- exists.

[0087] as well as The preparation method of the functional modifier comprises the following steps: S21, ethyl methacrylate, tert-butyl vinyl carbonate VV10, styrene, lauryl acrylate, initiator AIBN were added to N,N-dimethylformamide, the temperature was raised to 90°C, and stirred for 6 hours; after the reaction was completed, the mixture was distilled under reduced pressure and dried under vacuum at 60°C for 6 hours to obtain the target product ( ), that is, the functional modifier.

[0088] The usage ratio of (glycidyloxy)ethyl methacrylate, versatate VV10, styrene, lauryl acrylate, initiator AIBN, and N,N-dimethylformamide is 0.5g:5.5g:2.0g:2.0g:0.2g:100mL.

[0089] Its infrared data are as follows: 3011cm -1 、1595cm -1 、1498cm -1 : benzene ring exists; 1735cm -1 :-C=O exists; 1623cm -1 :-C=C- does not exist; 1605 cm -1 、811cm -1 :-C=C- does not exist; 1262cm -1 、927cm -1 、794cm -1 : Epoxy group exists.

[0090] The PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 1.5:1.

[0091] The PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:2.0.

[0092] The pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:3.0.

[0093] A method for preparing PP material for a turnover box comprises the following steps: S31, mixing; PP, macromolecular compatibilizer and functional modifier were added into a mixer, and stirred at a stirring rate of 300 r / min for 30 min to obtain component I; other raw materials in the formula were stirred at a stirring rate of 800 r / min for 10 min to obtain component II; S32, extrusion; Component I in S31 is added from the main feeding port of the extruder, and component II is added from the side feeding port, and melt blended and extruded; The extruder has a screw length-to-diameter ratio of 60:1 and a screw speed of 316 rpm; and The temperatures of the screw sections of the extruder are 185°C in zone 1, 195°C in zone 2, 200°C in zone 3, 200°C in zone 4, 200°C in zone 5, 203°C in zone 6, 205°C in zone 7, 212°C in zone 8, 215°C in zone 9, 220°C in zone 10, 220°C in zone 11, and 2015°C in zone 12; The side feed port is located in the third zone of the extruder.

[0094] S33, granulation; The melt in S32 is subjected to the processes of strand drawing, cooling and pelletizing to obtain PP material for turnover boxes.

[0095] The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 1:1.

[0096] The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 2:1.

[0097] The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:1.0.

[0098] The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:3.0.

[0099] The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:2.0.

[0100] The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:4.0.

[0101] The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The preparation method of the toughening agent, in S11, The silane coupling agent KH171 was replaced with silane coupling agent KH570.

[0102] The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The method for preparing the functional modifier, in S21, The versatate VV10 was replaced by versatate VV9.

[0103] The following comparative examples are compared with specific embodiment 1: Comparative Example 1 The rest is the same as in Example 1, except that: A PP material for turnover boxes, No toughening agent was added to the formulation.

[0104] Comparative Example 2 The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The toughening agent was replaced with POE.

[0105] Comparative Example 3 The rest is the same as in Example 1, except that: A PP material for turnover boxes, No functional modifiers were added to the formulation.

[0106] Comparative Example 4 The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The method for preparing the functional modifier, in S21, The usage ratio of (glycidyloxy)ethyl methacrylate, versatate VV10, methyl methacrylate, isooctyl acrylate, initiator AIBN, and N,N-dimethylformamide is 0g:5.0g:1.5g:3.5g:0.2g:100mL; that is, no (glycidyloxy)ethyl methacrylate is added.

[0107] Comparative Example 5 The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The method for preparing the functional modifier, in S21, The usage ratio of (glycidyloxy)ethyl methacrylate, versatate VV10, methyl methacrylate, isooctyl acrylate, initiator AIBN, and N,N-dimethylformamide is 0.8g: 0g: 1.5g: 7.7g: 0.2g: 100mL; that is, versatate VV10 is not added.

[0108] Comparative Example 6 The rest is the same as in Example 1, except that: A PP material for turnover boxes, No macromolecular compatibilizer is added to the formulation.

[0109] Comparative Example 7 The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 0.5:1.

[0110] Comparative Example 8 The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 2.5:1.

[0111] Comparative Example 9 The rest is the same as in Example 1, except that: A PP material for turnover boxes, No PE was added to the formulation.

[0112] Comparative Example 10 The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:0, that is, no LLDPE is added.

[0113] Comparative Example 11 The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:4.0.

[0114] Comparative Example 12 The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:1.0.

[0115] Comparative Example 13 The rest is the same as in Example 1, except that: In a PP material formula for turnover boxes, The pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:5.0.

[0116] Comparative Example 14 The rest is the same as in Example 1, except that: A method for preparing PP material for a turnover box, in step S32, All raw materials are added from the main feeding port for extrusion.

[0117] The turnover boxes prepared in the embodiments of the present invention and the comparative examples were respectively measured by injection molding with PP material into standard specimens, and tested according to the standards. The results are shown in Table 1.

[0118] Table 1 Physical test performance of each embodiment First, it can be concluded from Examples 1-11 in Table 1 that the PP material for turnover boxes of the present invention has excellent mechanical properties and thermal properties; specifically, it has excellent impact resistance, heat resistance, wear resistance and aging resistance; it is reflected in having high notched impact strength, heat deformation temperature, low wear rate and high aging performance retention rate.

[0119] From Example 1 and Comparative Examples 1-2, it can be observed that the PP material for the turnover box in the present invention uses a homemade toughening agent, which has excellent strengthening and toughening effects; from Example 1 and Comparative Examples 3-5, it can be observed that the PP material for the turnover box in the present invention uses a homemade functional modifier, which has excellent aging resistance and a certain toughening effect; from Example 1 and Comparative Example 6, it can be observed that the macromolecular compatibilizer has a positive significance for improving the mechanical properties of the material; from Example 1 and Comparative Examples 7-8, it can be observed that the use of homopolymer PP and copolymer PP has a synergistic effect. Use, improve mechanical properties and thermal properties; from Example 1 and comparative examples 9-11, it can be observed that the use of HDPE and LLDPE compound, the LLDPE with improved mechanical properties and flexibility also has impact resistance; and can improve the compatibility with POE, and effectively play the role of POE in strengthening and toughening; from Example 1 and comparative examples 12-13, it can be observed that the appropriate ratio of pigments and fillers can have a positive effect on anti-aging and impact resistance; from Example 1 and comparative example 14, it can be observed that the side feeding process plays an important role in improving the comprehensive performance of the material.

[0120] In summary, the PP material for turnover boxes of the present invention has excellent impact resistance, aging resistance and wear resistance through formula design and process design optimization, and has great practical significance.

[0121] The test method is as follows: (1) Tensile strength: tested according to the method described in GB / T1040.2-2006; the tensile rate is 50 mm / min.

[0122] (2) Elongation at break: Tested according to the method described in GB / T1040.2-2006; the tensile rate is 50 mm / min.

[0123] (3) Notched impact strength: tested according to the method described in GB / T 1843.1-2008.

[0124] (4) Heat deformation temperature: Tested in accordance with the method described in GB / T 1634.2-2004; using 0.45 MPa bending stress B method.

[0125] (5) Wear rate: The mass wear rate is tested according to the method described in GB / T 3960-2016.

[0126] (6) Performance retention rate after aging (aging resistance): According to GB / T 16422-2022, the sample is subjected to accelerated aging with a xenon lamp for 1000 hours, the material performance is tested, and the retention rate is calculated.

[0127] Based on the above ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above description. The technical scope of the present invention is not limited to the contents of the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A PP material for turnover box, characterized in that: The invention comprises the following raw materials in parts by weight: PP 50-75 copies; PE 5-25 parts; 4.0-6.0 parts of toughening agent; 1.0-2.0 parts of macromolecular compatibilizer; Functional modifier 2.0-4.0 parts; 15-30 parts of pigments and fillers; Antioxidant 0.3-1.0 part; Light stabilizer 0.2-0.6 parts; Lubricant 0.2-0.5 parts; The preparation method of the toughening agent comprises the following steps: S11, surface-modifying calcium carbonate with a silane coupling agent containing a carbon-carbon double bond to obtain an intermediate product; The usage ratio of calcium carbonate to the silane coupling agent containing a carbon-carbon double bond is 1g:3.5-5.5g; S12, mixing and granulating the intermediate product, maleic anhydride, POE and DCP to obtain a target product, i.e., the toughening agent; The usage ratio of the intermediate product, maleic anhydride, POE and DCP is 10g: 0.5-1.5g: 10-20g: 0.05g; as well as The preparation method of the functional modifier comprises the following steps: S21, free radical polymerization of epoxy olefins, versatile vinyl carbonate, hard monomers, and soft monomers to obtain a target product, namely, the functional modifier; The usage ratio of the epoxy olefins, versatile vinyl carbonate, hard monomer and soft monomer is 0.5-1.0g: 4.5-5.5g: 1.0-2.0g: 2.0-3.5g.

2. The PP material for turnover box according to claim 1, characterized in that: The calcium carbonate particle size is 2000-3000 mesh; and The silane coupling agent containing carbon-carbon double bonds is vinyl silane or acryloxy silane.

3. The PP material for turnover box according to claim 1, characterized in that: The melt index of the POE is 5-10 g / 10 min.

4. The PP material for turnover box according to claim 1, characterized in that: The versatile vinyl carbonate is VV10 or VV9; The hard monomer is methyl methacrylate or styrene; and The soft monomer is butyl acrylate, isooctyl acrylate or lauryl acrylate.

5. The PP material for turnover box according to claim 1, characterized in that: The PP is a mixture of copolymer PP and homopolymer PP in a mass ratio of 1.0-2.0:1; and The melt index of the copolymer PP is 60-100 g / 10 min; the melt index of the homopolymer PP is 25-30 g / 10 min.

6. The PP material for turnover box according to claim 1, characterized in that: The PE is a mixture of HDPE and LLDPE in a mass ratio of 1.0:1.0-3.

0.

7. The PP material for turnover box according to claim 1, characterized in that: The macromolecular compatibilizer is PP-g-MAH.

8. The PP material for turnover box according to claim 1, characterized in that: The pigment and filler are titanium dioxide and talcum powder added in a mass ratio of 1.0:2.0-4.0; and The titanium dioxide is rutile titanium dioxide.

9. A method for preparing PP material for turnover box, characterized in that: The following steps are involved: S31, mixing; The PP, macromolecular compatibilizer and functional modifier are mixed evenly to obtain component I; the other raw materials in the formula are mixed evenly to obtain component II; S32, extrusion; Component I in S31 is added from the main feeding port of the extruder, and component II is added from the side feeding port, and melt blended and extruded; S33, granulation; The melt in S32 is subjected to the processes of strand drawing, cooling and pelletizing to obtain PP material for turnover boxes.

10. The preparation method according to claim 9, characterized in that: The extruder has a screw length-to-diameter ratio of 50-60:1 and a rotation speed of 300-400 rpm; and The temperatures of the screw sections of the extruder are 175-185°C in zone 1, 185-195°C in zone 2, 190-200°C in zone 3, 190-200°C in zone 4, 190-200°C in zone 5, 195-205°C in zone 6, 195-205°C in zone 7, 205-215°C in zone 8, 205-215°C in zone 9, 210-220°C in zone 10, 210-220°C in zone 11, and 205-215°C in zone 12; The side feed port is located in the third zone or the fourth zone of the extruder.

Images