A high-melting and high-impact polyethylene material and preparation method thereof

Abstract

The present invention provides a high-melting and high-impact polypropylene material and a preparation method thereof, and relates to the technical field of polypropylene materials. The polypropylene material provided by the present invention comprises the following components by mass: 25-45 parts of polyethylene automobile recycled materials, 45-65 parts of polyethylene barrel recycled materials, 0.1-2 parts of carbon black, 0.05-1.5 parts of modified antioxidants, 0.1-0.5 parts of modified toughening agents and 0.1-1.5 parts of lubricants. Its preparation method is: S1: polyethylene automobile recycled materials, polyethylene barrel recycled materials and carbon black are premixed to obtain a premix; S2: the premix is ​​mixed with a modified antioxidant, a toughening agent and a lubricant in an extruder, melt-extruded, and granulated. The polypropylene material prepared by the present invention significantly improves its fluidity while ensuring the impact strength of the product.

Description

Technical Field

[0001] The invention relates to the technical field of polyethylene materials, and in particular to a high-melting and high-impact polyethylene material and a preparation method thereof. Background Art

[0002] High-impact polyethylene materials are often accompanied by problems such as low melt index and poor rigidity. In order to improve the availability of the material and increase the fluidity of the material, the researchers of the present invention have developed a high melt index and high-impact polyethylene material and a preparation method thereof, using recycled PE as raw material. By optimizing the preparation method, the problem of high-impact material fluidity is solved and the availability of the material is increased. Summary of the invention

[0003] In view of the above problems, the present invention provides a high-melting and high-impact polyethylene material and a preparation method thereof. By using recycled PE as the main raw material, optimizing the components and preparation process, the fluidity of the high-impact material is improved while ensuring the impact strength of the material.

[0004] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0005] On the one hand, the present invention provides a high-melting and high-impact polyethylene material, which comprises the following components by mass: 25-45 parts of polyethylene automobile recycled materials, 45-65 parts of polyethylene barrel recycled materials, 0.1-2 parts of carbon black, 0.05-1.5 parts of modified antioxidants, 0.1-0.5 parts of modified toughening agents and 0.1-1.5 parts of lubricants.

[0006] Preferably, the high-melting and high-impact polyethylene material comprises the following components by mass: 30-40 parts of polyethylene automobile recycled materials, 50-60 parts of polyethylene barrel recycled materials, 0.5-1 part of carbon black, 0.1-1 part of modified antioxidant, 0.2-0.4 part of modified toughening agent and 0.5-1 part of lubricant.

[0007] Further preferably, the high-melting and high-impact polyethylene material comprises the following components by mass: 32-38 parts of polyethylene automobile recycled materials, 50-55 parts of polyethylene barrel recycled materials, 0.5-0.8 parts of carbon black, 0.5-1 parts of modified antioxidants, 0.3-0.4 parts of modified toughening agents and 0.8-1 parts of lubricants.

[0008] More preferably, the high-melting and high-impact polyethylene material comprises the following components by mass: 36 parts of polyethylene automobile recycled materials, 54 parts of polyethylene barrel recycled materials, 0.8 parts of carbon black, 1 part of modified antioxidant, 0.4 parts of modified toughening agent and 0.8 parts of lubricant.

[0009] Preferably, the raw materials of the modified antioxidant include polypropylene resin, antioxidant, light stabilizer and polyethylene wax.

[0010] Preferably, the antioxidant is pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (1010) and tris(2,4-di-tert-butylphenyl) phosphite (168).

[0011] Preferably, the mass ratio of the tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester (1010) to tris(2,4-di-tert-butylphenyl)phosphite (168) is 1:1.2-2.4; further preferably, the mass ratio of the tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pentaerythritol ester (1010) to tris(2,4-di-tert-butylphenyl)phosphite (168) is 1:1.8.

[0012] Preferably, the light stabilizer is selected from at least one of hydroxyethylpiperidinol bis[β-(3-methyl-5-tert-butyl-4-hydroxyphenyl)]propionate and UV770; further preferably, the light stabilizer is hydroxyethylpiperidinol bis[β-(3-methyl-5-tert-butyl-4-hydroxyphenyl)]propionate.

[0013] Preferably, the mass ratio of the polypropylene resin, antioxidant, light stabilizer and polyethylene wax is 30-40:50-60:15-25:0.1-1; further preferably, the mass ratio of the polypropylene resin, antioxidant, light stabilizer and polyethylene wax is 30-35:55-60:15-20:0.1-0.5; more preferably, the mass ratio of the polypropylene resin, antioxidant, light stabilizer and polyethylene wax is 32:58:16:0.2.

[0014] Preferably, the preparation method of the hydroxyethyl piperidinol bis[β-(3-methyl-5-tert-butyl-4-hydroxyphenyl)] propionate is: using hydroxyethyl piperidinol and β-(3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate as raw materials and lithium acetate as a catalyst for the reaction, and the molar ratio of the hydroxyethyl piperidinol to β-(3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate is 1:1.5-1.8.

[0015] More preferably, the molar ratio of hydroxyethylpiperidinol to β-(3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate is 1:1.8.

[0016] Preferably, the preparation method of the modified antioxidant is: polypropylene resin, antioxidant, light stabilizer and polyethylene wax are evenly mixed, and stirred at 60-70° C. for 1-3 hours.

[0017] Preferably, the modified toughening agent comprises styrene-ethylene-butylene-styrene block copolymer (SEBS), maleic anhydride and montmorillonite.

[0018] Preferably, the mass ratio of the styrene-ethylene-butylene-styrene block copolymer (SEBS), maleic anhydride and montmorillonite is 90-95:3-8:1-3;

[0019] Further preferably, the mass ratio of the styrene-ethylene-butylene-styrene block copolymer (SEBS), maleic anhydride and montmorillonite is 92:5:2;

[0020] Preferably, the modified toughening agent is prepared by mixing styrene-ethylene-butylene-styrene block copolymer (SEBS), maleic anhydride and montmorillonite, and melt-extruding the mixture.

[0021] Preferably, the extrusion temperature is 190-210° C., and the screw speed is 30-50 r / min; further preferably, the extrusion temperature is 195° C., and the screw speed is 50 r / min.

[0022] Preferably, the lubricant is at least one of erucamide and phenolic resin; more preferably, the lubricant is erucamide and phenolic resin.

[0023] Preferably, the mass ratio of erucamide to phenolic resin is 2-3:5-6; further preferably, the mass ratio of erucamide to phenolic resin is 2-2.5:5-5.5; more preferably, the mass ratio of erucamide to phenolic resin is 2.4:5.2.

[0024] In another aspect, the present invention provides a method for preparing the above-mentioned high-melting high-impact polyethylene material, comprising the following steps:

[0025] S1: premixing polyethylene automobile recycled material, polyethylene barrel recycled material and carbon black to obtain a premix;

[0026] S2: The premix is ​​mixed with the modified antioxidant, toughening agent and lubricant in an extruder, melt-extruded and granulated.

[0027] Preferably, the premixing temperature in S1 is 70-90° C., so that the polyethylene automobile recycled material, the polyethylene barrel recycled material and the carbon black are evenly mixed.

[0028] Preferably, the extruder described in S2 comprises 6 temperature control zones, the temperature of temperature control zone 1 is 180-190°C, the temperature of temperature control zone 2 is 192-205°C, the temperature of temperature control zone 3 is 205-215°C, the temperature of temperature control zone 4 is 205-215°C, the temperature of temperature control zone 5 is 185-195°C, and the temperature of temperature control zone 6 is 175-185°C;

[0029] Further preferably, the extruder described in S2 comprises 6 temperature control zones, the temperature of temperature control zone 1 is 185-190°C, the temperature of temperature control zone 2 is 192-200°C, the temperature of temperature control zone 3 is 205-210°C, the temperature of temperature control zone 4 is 205-210°C, the temperature of temperature control zone 5 is 185-190°C, and the temperature of temperature control zone 6 is 175-180°C;

[0030] More preferably, the extruder described in S2 includes 6 temperature control zones, the temperature of temperature control zone 1 is 190°C, the temperature of temperature control zone 2 is 195°C, the temperature of temperature control zone 3 is 210°C, the temperature of temperature control zone 4 is 210°C, the temperature of temperature control zone 5 is 190°C, and the temperature of temperature control zone 6 is 180°C.

[0031] Preferably, the screw speed of the extruder described in S2 is 30-45r / min; further preferably, the screw speed of the extruder described in S2 is 30-40r / min; more preferably, the screw speed of the extruder described in S2 is 36r / min.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1. The technical solution of the present invention prepares the modified oxidant by using the components and specific ratios of antioxidant, polypropylene resin, light stabilizer and lubricant, which not only improves the antioxidant property of the product, but also improves the compatibility of each component with the main material polyethylene automobile recycled material and polyethylene barrel recycled material, thereby improving the fluidity of the product.

[0034] 2. The technical solution of the present invention greatly improves the compatibility with the main material by modifying SEBS with maleic anhydride and montmorillonite, thereby improving the fluidity of the product while ensuring its impact strength.

[0035] 3. The technical solution of the present invention improves the fluidity of the product while ensuring its impact strength by optimizing the components, selecting specific modified antioxidants, modified toughening agents and lubricants, and optimizing the distribution ratio of the components. DETAILED DESCRIPTION

[0036] In order to make the technical means, creative features, purpose and effect of the present invention easy to understand, the present invention is further explained below in conjunction with specific embodiments, but the following embodiments are only preferred embodiments of the present invention, not all. Based on the embodiments in the implementation mode, other embodiments obtained by those skilled in the art without making creative work all belong to the protection scope of the present invention. It is worth noting that the raw materials used in the present invention are all common commercial products, and their sources are not specifically limited. The technology and scientific terms used in the embodiments have the meanings commonly understood by those of ordinary skill in the art to which the present invention belongs.

[0037] Example 1

[0038] 1) Composition and ratio of high-melting and high-impact polyethylene materials:

[0039] The high-melting and high-impact polyethylene material comprises the following components by weight: 36 parts of polyethylene automobile recycled materials, 54 parts of polyethylene barrel recycled materials, 0.8 parts of carbon black, 1 part of modified antioxidant, 0.4 parts of modified toughening agent, 0.25 parts of erucic acid amide and 0.55 parts of phenolic resin.

[0040] The preparation method of the modified antioxidant:

[0041] a. Preparation of hydroxyethylpiperidinol bis[β-(3-methyl-5-tert-butyl-4-hydroxyphenyl)] propionate:

[0042] In a 100 mL round-bottom flask, 15 g of β-(3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate, 8.3 g of hydroxyethyl piperidinol, and 0.2 g of lithium acetate were added; the temperature was raised to 150°C, and the vacuum was reduced to maintain the vacuum degree between -0.08 and 0.09 MPa, and the reaction was continued for 2 hours; the vacuum was evacuated to 2 mmHg (267 Pa), and the reaction was continued for 1 hour; the temperature was lowered, 270 mL of 85% aqueous methanol was added, and the mixture was heated to dissolve, and then cooled to crystallize to obtain 17.2 g of hydroxyethyl piperidinol di-β-(3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate (I).

[0043] b. 32 parts of polypropylene resin, 20.7 parts of antioxidant 1010, 37.3 parts of antioxidant 168, 16 parts of hydroxyethylpiperidinol bis[β-(3-methyl-5-tert-butyl-4-hydroxyphenyl)]propionate and 0.2 parts of polyethylene wax were mixed evenly and stirred at 65° C. for 2 hours.

[0044] The preparation method of the modified toughening agent:

[0045] 92 parts of SEBS, 5 parts of maleic anhydride and 2 parts of montmorillonite were mixed and melt-extruded at an extrusion temperature of 195° C. and a screw speed of 50 r / min.

[0046] 2) Preparation

[0047] S1: Polyethylene automobile recycled material, polyethylene barrel recycled material and carbon black are premixed at 80°C and mixed to obtain a premix;

[0048] S2: The premix is ​​mixed with the modified antioxidant, toughening agent and lubricant in an extruder, melt-extruded and granulated; the extruder includes 6 temperature control zones, the temperature of temperature control zone 1 is 190°C, the temperature of temperature control zone 2 is 195°C, the temperature of temperature control zone 3 is 210°C, the temperature of temperature control zone 4 is 210°C, the temperature of temperature control zone 5 is 190°C, and the temperature of temperature control zone 6 is 180°C; the screw speed of the extruder is 36r / min.

[0049] A high-melting and high-impact polyethylene material is prepared.

[0050] Example 2

[0051] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0052] 1) Composition and ratio of high-melting and high-impact polyethylene materials:

[0053] The high-melting and high-impact polyethylene material comprises the following components by weight: 25 parts of polyethylene automobile recycled materials, 65 parts of polyethylene barrel recycled materials, 0.4 parts of carbon black, 1.5 parts of modified antioxidants, 0.1 parts of modified toughening agents, 0.48 parts of erucic acid amide and 1.02 parts of phenolic resin.

[0054] Example 3

[0055] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0056] 1) Composition and ratio of high-melting and high-impact polyethylene materials:

[0057] The high-melting and high-impact polyethylene material comprises the following components by weight: 45 parts of polyethylene automobile recycled materials, 45 parts of polyethylene barrel recycled materials, 2 parts of carbon black, 0.1 parts of modified antioxidants, 0.5 parts of modified toughening agents, 0.16 parts of erucic acid amide and 0.34 parts of phenolic resin.

[0058] Comparative Example 1

[0059] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0060] 1) Composition and ratio of high-melting and high-impact polyethylene materials:

[0061] The high-melting and high-impact polyethylene material comprises the following components by weight: 50 parts of polyethylene automobile recycled material, 35 parts of polyethylene barrel recycled material, 3 parts of carbon black, 2 parts of modified antioxidant, 0.6 parts of modified toughening agent, 0.7 parts of erucic acid amide and 0.5 parts of phenolic resin.

[0062] The remaining operations are the same as those in Example 1.

[0063] Comparative Example 2

[0064] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0065] The high-melting and high-impact polyethylene material comprises the following components by weight: 36 parts of polyethylene automobile recycled materials, 54 parts of polyethylene barrel recycled materials, 0.8 parts of carbon black, 1 part of modified antioxidant, 0.4 parts of modified toughening agent, and 0.8 parts of erucamide.

[0066] The remaining operations are the same as those in Example 1.

[0067] Comparative Example 3

[0068] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0069] The high-melting and high-impact polyethylene material comprises the following components by weight: 36 parts of polyethylene automobile recycled materials, 54 parts of polyethylene barrel recycled materials, 0.8 parts of carbon black, 1 part of modified antioxidant, 0.4 parts of modified toughening agent, and 0.8 parts of phenolic resin.

[0070] The remaining operations are the same as those in Example 1.

[0071] Comparative Example 4

[0072] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0073] The high-melting and high-impact polyethylene material comprises the following components by weight: 36 parts of polyethylene automobile recycled materials, 54 parts of polyethylene barrel recycled materials, 0.8 parts of carbon black, 1 part of antioxidant 1010, 0.4 parts of modified toughening agent, and 0.8 parts of phenolic resin.

[0074] The remaining operations are the same as those in Example 1.

[0075] Comparative Example 5

[0076] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0077] The high-melting and high-impact polyethylene material comprises the following components by weight: 36 parts of polyethylene automobile recycled materials, 54 parts of polyethylene barrel recycled materials, 0.8 parts of carbon black, 1 part of antioxidant 168, 0.4 parts of modified toughening agent, and 0.8 parts of phenolic resin.

[0078] The remaining operations are the same as those in Example 1.

[0079] Comparative Example 6

[0080] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0081] The high-melting and high-impact polyethylene material comprises the following components by weight: 36 parts of polyethylene automobile recycled materials, 54 parts of polyethylene barrel recycled materials, 0.8 parts of carbon black, 1 part of modified antioxidant, 0.4 parts of SEBS, and 0.8 parts of phenolic resin.

[0082] The remaining operations are the same as those in Example 1.

[0083] Comparative Example 7

[0084] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0085] 1) Composition and ratio of high-melting and high-impact polyethylene materials:

[0086] The high-melting and high-impact polyethylene material comprises the following components by weight: 36 parts of polyethylene automobile recycled materials, 54 parts of polyethylene barrel recycled materials, 0.8 parts of carbon black, 1 part of modified antioxidant, 0.2 parts of toughening agent SBS, 0.2 parts of toughening agent POE, 0.25 parts of erucic acid amide and 0.55 parts of phenolic resin.

[0087] The remaining operations are the same as those in Example 1.

[0088] Comparative Example 8

[0089] Compared with Example 1, only the components and proportions of the high-melting high-impact polyethylene material are changed:

[0090] 1) Composition and ratio of high-melting and high-impact polyethylene materials:

[0091] The high-melting and high-impact polyethylene material comprises the following components by weight: 36 parts of polyethylene automobile recycled materials, 54 parts of polyethylene barrel recycled materials, 1.8 parts of carbon black, 0.4 parts of modified toughening agent, 0.25 parts of erucic acid amide and 0.55 parts of phenolic resin.

[0092] The remaining operations are the same as those in Example 1.

[0093] Test Example 1

[0094] The mechanical properties and melt index of the high melting and high impact polyethylene materials of Examples 1-3 and Comparative Examples 1-8 are shown in Table 1. The melt index test conditions are 230° C. and a load of 2160 g.

[0095] Table 1. Mechanical properties test and melt index

[0096]

[0097] Compared with Example 1, Comparative Example 1 changes the component ratio of the high-melting high-impact polyethylene material; Comparative Example 2 changes the component of the high-melting high-impact polyethylene material, and replaces the phenolic resin with erucic acid amide; Comparative Example 3 changes the component of the high-melting high-impact polyethylene material, and replaces erucic acid amide with phenolic resin; Comparative Examples 4-5 replace the antioxidant of the technical solution of the present invention; Comparative Examples 6-7 replace the toughening agent of the technical solution of the present invention; Comparative Example 8 does not add an antioxidant; Compared with the embodiments, the flow properties of the comparative examples are significantly reduced, and the impact strength is reduced by more than 10%, which proves that the technical solution of the present invention selects specific modified antioxidants, modified toughening agents and lubricants, and optimizes the ratio of each component, while ensuring the impact strength of the product, while improving its flowability.

[0098] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A high melting point and high impact polyethylene material, characterized in that: The composition comprises the following components by weight: 25-45 parts of polyethylene automobile recycled materials, 45-65 parts of polyethylene barrel recycled materials, 0.1-2 parts of carbon black, 0.05-1.5 parts of modified antioxidant, 0.1-0.5 parts of modified toughening agent and 0.1-1.5 parts of lubricant; The raw materials of the modified antioxidant include polypropylene resin, antioxidant, light stabilizer and polyethylene wax; The antioxidant is tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester and tris(2,4-di-tert-butylphenyl) phosphite; the mass ratio of the tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester and tris(2,4-di-tert-butylphenyl) phosphite is 1:1.2-2.4; The light stabilizer is hydroxyethylpiperidinol bis[β-(3-methyl-5-tert-butyl-4-hydroxyphenyl)] propionate; The mass ratio of the polypropylene resin, antioxidant, light stabilizer and polyethylene wax is 30-40:50-60:15-25:0.1-1; The preparation method of hydroxyethyl piperidinol bis[β-(3-methyl-5-tert-butyl-4-hydroxyphenyl)] propionate is as follows: hydroxyethyl piperidinol and β-(3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate are used as raw materials, lithium acetate is used as a catalyst for reaction, and the molar ratio of hydroxyethyl piperidinol to β-(3-methyl-5-tert-butyl-4-hydroxyphenyl) propionate is 1:1.5-1.8; The lubricant is erucic acid amide and phenolic resin; the mass ratio of erucic acid amide to phenolic resin is 2-3:5-6; The preparation method of the modified antioxidant is as follows: polypropylene resin, antioxidant, light stabilizer and polyethylene wax are evenly mixed, and stirred at 60-70° C. for 1-3 hours.

2. The high melting point and high impact polyethylene material according to claim 1, characterized in that: The modified toughening agent comprises styrene-ethylene-butylene-styrene block copolymer, maleic anhydride and montmorillonite; the mass ratio of the styrene-ethylene-butylene-styrene block copolymer, maleic anhydride and montmorillonite is 90-95:3-8:1-3.

3. The method for preparing the high melting point and high impact polyethylene material according to any one of claims 1 to 2, characterized in that: The following steps are involved: S1: premixing polyethylene automobile recycled material, polyethylene barrel recycled material and carbon black to obtain a premix; S2: The premix is ​​mixed with the modified antioxidant, toughening agent and lubricant in an extruder, melt-extruded and granulated.

4. The preparation method according to claim 3, characterized in that: The extruder described in S2 includes 6 temperature control zones, the temperature of temperature control zone 1 is 180-190°C, the temperature of temperature control zone 2 is 192-205°C, the temperature of temperature control zone 3 is 205-215°C, the temperature of temperature control zone 4 is 205-215°C, the temperature of temperature control zone 5 is 185-195°C, and the temperature of temperature control zone 6 is 175-185°C; the screw speed of the extruder described in S2 is 30-45r / min.

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