THERMOPLASTIC CROSSLINKED POLYETHYLENE MATERIAL, PREPARATION METHOD AND USE THEREOF

Abstract

The present application belongs to the field of polymer materials, discloses a thermoplastic crosslinked polyethylene material, preparation method and use thereof. The thermoplastic crosslinked polyethylene material comprises a first polyethylene component that is easily crosslinked, a second polyethylene component that is not easily crosslinked, and an organic peroxide crosslinking agent. In the present application, the product of the first polyethylene that is easily crosslinked, is crosslinked in a fine particle form and uniformly dispersed in the second polyethylene component that is not easily crosslinked, and intertwined with the macromolecular chain of the second polyethylene component that is not easily crosslinked. The resulted product is completely thermoplastic, and has properties, such as heat resistance and creep property, superior to the first polyethylene component that is easily crosslinked and the second polyethylene component that is not easily crosslinked.

Claims

1. A thermoplastic crosslinked polyethylene material, wherein the thermoplastic crosslinked polyethylene material comprises the following raw materials in parts by weight: 3070 parts of a first polyethylene component; 3070 parts of a second polyethylene component; and 0.150.35 part of a crosslinking agent; the first polyethylene component is an ethylene homopolymer free of antioxidants or other free radical scavengers; the second polyethylene component is an ethylene homopolymer containing antioxidants or other free radical scavengers, or a copolymer of ethylene and a non-ethylene monomer.

2. The thermoplastic crosslinked polyethylene material according to claim 1, wherein the non-ethylene monomer is one or more of butene, hexene and octene.

3. The thermoplastic crosslinked polyethylene material according to claim 1, wherein the thermoplastic crosslinked polyethylene material comprises the following raw materials in parts by weight: 35 parts of the first polyethylene component; 65 parts of the second polyethylene component; and 0.25 part of an organic peroxide crosslinking agent; the first polyethylene component is an ethylene homopolymer free of antioxidants or other free radical scavengers; the second polyethylene component is a copolymer of ethylene and hexene monomer.

4. The thermoplastic crosslinked polyethylene material according to claim 3, wherein the organic peroxide crosslinking agent is one or more of di-tert-butane peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne or di-tert-butylperoxy diisopropylbenzene.

5. The thermoplastic crosslinked polyethylene material according to claim 1, further comprising an antioxidant, the antioxidant is dilauryl thiodipropionate and/or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

6. The thermoplastic crosslinked polyethylene material according to claim 1, comprising one or more of a conductive auxiliary agent, a heat conduction auxiliary agent, a flame retardant and a flow improver.

7. A method of preparing the thermoplastic crosslinked polyethylene material according to claim 1, comprising the step of heating melt-plasticized extrusion pellets after mixing the raw materials.

8. The method of claim 7, further comprising the step of heating a melt to a temperature of 240 C. to 250 C. for extrusion.

9. (canceled)

10. A method of preparing pipes, plates, sheets, bars, hollow containers and mechanical parts, comprising the step of using the thermoplastic crosslinked polyethylene material according to claim 1, the thermoplastic crosslinked polyethylene material obtained by heating melt-plasticized extrusion pellets after mixing the raw materials for preparing pipes, plates, sheets, bars, hollow containers and mechanical parts.

11. The thermoplastic crosslinked polyethylene material according to claim 2, wherein the thermoplastic crosslinked polyethylene material comprises the following raw materials in parts by weight: 35 parts of the first polyethylene component; 65 parts of the second polyethylene component; and 0.25 part of an organic peroxide crosslinking agent; the first polyethylene component is an ethylene homopolymer free of antioxidants or other free radical scavengers; the second polyethylene component is a copolymer of ethylene and hexene monomer.

12. The thermoplastic crosslinked polyethylene material according to claim 2, further comprising an antioxidant, the antioxidant is dilauryl thiodipropionate and/or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

13. The thermoplastic crosslinked polyethylene material according to claim 3, further comprising an antioxidant, the antioxidant is dilauryl thiodipropionate and/or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

14. The thermoplastic crosslinked polyethylene material according to claim 4, further comprising an antioxidant, the antioxidant is dilauryl thiodipropionate and/or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

15. The thermoplastic crosslinked polyethylene material according to claim 10, further comprising an antioxidant, the antioxidant is dilauryl thiodipropionate and/or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

16. The thermoplastic crosslinked polyethylene material according to claim 2, comprising one or more of a conductive auxiliary agent, a heat conduction auxiliary agent, a flame retardant and a flow improver.

17. The thermoplastic crosslinked polyethylene material according to claim 3, comprising one or more of a conductive auxiliary agent, a heat conduction auxiliary agent, a flame retardant and a flow improver.

18. The thermoplastic crosslinked polyethylene material according to claim 4, comprising one or more of a conductive auxiliary agent, a heat conduction auxiliary agent, a flame retardant and a flow improver.

19. The thermoplastic crosslinked polyethylene material according to claim 5, comprising one or more of a conductive auxiliary agent, a heat conduction auxiliary agent, a flame retardant and a flow improver.

20. The thermoplastic crosslinked polyethylene material according to claim 10, comprising one or more of a conductive auxiliary agent, a heat conduction auxiliary agent, a flame retardant and a flow improver.

21. The thermoplastic crosslinked polyethylene material according to claim 11, comprising one or more of a conductive auxiliary agent, a heat conduction auxiliary agent, a flame retardant and a flow improver.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0031] The technical solution of the present application will be described clearly and completely hereinafter, and it is obvious that the described examples are a part of the examples of the present application, but not all of the examples of the present application. Based on the examples of the present application, all other examples obtained by one skilled in the art without creative efforts are within the scope of the present application. Further, the technical features involved in the different embodiments of the present application described below may be combined with each other as long as they do not constitute a conflict with each other.

[0032] In the following examples, DTBP is di-tert-butane peroxide, DYBP is 2,5-dimethyl-2,5-di-tert-butylperoxy-3-hexyne, antioxidant 1076 is octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, antioxidant 1010 is tetrakis[-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] pentaerythritol ester, antioxidant DLTP is dilauryl thiodipropionate, DLTDP is dilauryl thiodipropionate, BIBP is di-tert-butylperoxy diisopropylbenzene, which is a peroxide crosslinking agent, and KT-12A is PE-g-MAH, that is a maleic anhydride grafted polyethylene resin.

Example 1

[0033] Example 1 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 300 g of HDPE, 700 g of PERT, 2.3 g of DTBP, 2.5 g of antioxidant 1076, and 1.5 g of DLTDP.

[0034] In the above raw materials, HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; PERT is heat resistant polyethylene, which is a copolymer of ethylene monomer and hexene monomer, and is purchased from Sinopec Qilu Petrochemical Company.

[0035] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is as follows:

[0036] The raw materials were weighed according to the above formula, and mixed in a high-speed mixer for 10 minutes. The resulted mixed raw material was put into a twin-screw extrusion granulator for granulating, thereby obtaining the thermoplastic crosslinked polyethylene particles. In this example, the rotate speed of the extruder was 30 rpm, and the temperatures of each section of the extruder were 160 C., 180 C., 200 C., 230 C. and 240 C., respectively.

Example 2

[0037] Example 2 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 350 g of HDPE, 650 g of PERT, 2.5 g of DTBP, 2.0 g of antioxidant 1076, and 2.0 g of DLTDP.

[0038] In the above raw materials, HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; PERT is heat resistant polyethylene, which is a copolymer of ethylene monomer and hexene monomer, and is purchased from Sinopec Qilu Petrochemical Company.

[0039] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is as follows:

[0040] The raw materials were weighed according to the above formula, and mixed in a high-speed mixer for 10 minutes. The resulted mixed raw material was put into a twin-screw extrusion granulator for granulating, thereby obtaining the thermoplastic crosslinked polyethylene particles. In this example, the rotate speed of the extruder was 40 rpm, and the temperatures of each section of the extruder were 160 C., 180 C., 200 C., 230 C. and 245 C., respectively.

Example 3

[0041] Example 3 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 450 g of HDPE, 550 g of PERT, 2.8 g of DTBP, 2.5 g of antioxidant 1076, and 2.0 g of DLTDP.

[0042] In the above raw materials, HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; PERT is heat resistant polyethylene, which is a copolymer of ethylene monomer and hexene monomer, and is purchased from Sinopec Qilu Petrochemical Company.

[0043] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is as follows:

[0044] The raw materials were weighed according to the above formula, and mixed in a high-speed mixer for 10 minutes. The resulted mixed raw material was put into a twin-screw extrusion granulator for granulating, thereby obtaining the thermoplastic crosslinked polyethylene particles. In this example, the rotate speed of the extruder was 50 rpm, and the temperatures of each section of the extruder were 160 C., 180 C., 200 C., 230 C. and 250 C., respectively.

Example 4

[0045] Example 4 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 350 g of MDPE, 650 g of PERT, 2.5 g of DTBP, 2.0 g of antioxidant 1076, and 2.5 g of DLTDP.

[0046] In the above raw materials, MDPE is medium density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; PERT is heat resistant polyethylene, which is a copolymer of ethylene monomer and hexene monomer, and is purchased from Sinopec Qilu Petrochemical Company.

[0047] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is the same as one in Example 1.

Example 5

[0048] Example 5 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 300 g of HDPE, 700 g of PERT, 1.5 g of DYBP, and 4.2 g of antioxidant 1076.

[0049] In the above raw materials, HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; PERT is heat resistant polyethylene, which is a copolymer of ethylene monomer and hexene monomer, and is purchased from Sinopec Qilu Petrochemical Company.

[0050] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is the same as one in Example 3.

Example 6

[0051] Example 6 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 350 g of HDPE, 650 g of PERT, 2.5 g of DTBP, and 4.2 g of antioxidant 1076.

[0052] In the above raw materials, HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; PERT is heat resistant polyethylene, which is a copolymer of ethylene monomer and hexene monomer, and is purchased from Sinopec Qilu Petrochemical Company.

[0053] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is the same as one in Example 3.

Example 7

[0054] Example 7 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 400 g of HDPE, 600 g of PERT, 2.8 g of DTBP, and 4.2 g of antioxidant 1076.

[0055] In the above raw materials, HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; PERT is heat resistant polyethylene, which is a copolymer of ethylene monomer and hexene monomer, and is purchased from Sinopec Qilu Petrochemical Company.

[0056] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is the same as one in Example 3.

Example 8

[0057] Example 8 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 500 g of HDPE, 500 g of PERT, 3.0 g of DTBP, and 4.2 g of antioxidant 1076.

[0058] In the above raw materials, HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; PERT is heat resistant polyethylene, which is a copolymer of ethylene monomer and hexene monomer, and is purchased from Sinopec Qilu Petrochemical Company.

[0059] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is the same as one in Example 3.

Example 9

[0060] Example 9 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 600 g of MDPE, 400 g of PERT, 3.5 g of DYBP, and 4.2 g of antioxidant 1076.

[0061] In the above raw materials, MDPE is medium density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; PERT is heat resistant polyethylene, which is a copolymer of ethylene monomer and hexene monomer, and is purchased from Sinopec Qilu Petrochemical Company.

[0062] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is the same as one in Example 3.

Example 10

[0063] Example 10 provides a thermoplastic crosslinked polyethylene material, comprising the raw materials of 600 g of LDPE, 300 g of HDPE+ antioxidant 1010+ antioxidant DLTP, 3.5 g of BIBP, and 4.2 g of antioxidant 1076.

[0064] In the above raw materials, LDPE is low density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd. In order to make HDPE have a property of being not easily crosslinked, an appropriate amount of antioxidants 1010 and DLTP are added to HDPE, the appropriate amount is 0.5% by weight of HDPE, respectively. Among them, antioxidant 1010 is used as a primary antioxidant, and antioxidant DLTP is used as a secondary antioxidant, both of them have an excellent free radical scavenging ability.

[0065] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is as follows:

[0066] HDPE, antioxidants 1010 and DLTP were mixed and melt granulated, and then other components of the raw materials were added therein and mixed in a high-speed mixer for 10 minutes. The resulted mixed raw material was put into a twin-screw extrusion granulator for granulating, thereby obtaining the thermoplastic crosslinked polyethylene particles. In this example, the rotate speed of the extruder was 50 rpm, and the temperatures of each section of the extruder were 160 C., 180 C., 200 C., 230 C. and 250 C., respectively.

Example 11

[0067] Example 11 provides a flame-retardant thermoplastic crosslinked polyethylene material, comprising the raw materials of 350 g of HDPE, 650 g of mLLDPE, 2.5 g of BIBP, 2.5 g of antioxidant 1076, 2.0 g of DLTDP, 430 g of HFR23, and 15 g of white oil.

[0068] In the above raw materials, HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; mLLDPE is metallocene linear low density polyethylene, which is a copolymer of ethylene monomer and hexene monomer containing an appropriate amount of antioxidants. The copolymer is imported from abroad, and purchased from ExxonMobil 3518GA.

[0069] The specific method of preparing thermoplastic crosslinked polyethylene particles using the above raw materials is the same as one in Example 3.

Example 12

[0070] Example 12 provides a thermally conductive thermoplastic crosslinked polyethylene material, comprising the raw materials of 350 g of HDPE, 650 g of mLLDPE, 2.5 g of BIBP, 2.5 g of antioxidant 1076, 2.0 g of DLTDP, 220 g of graphite, 60 g of KT-12A, and 12 g of white oil.

[0071] In the above raw materials, HDPE is high density polyethylene, which contains no antioxidant or other radical scavenger, and is purchased from Sinopec Yangzi Petrochemical Co., Ltd.; mLLDPE is metallocene linear low density polyethylene, which is a copolymer of ethylene monomer and hexene monomer containing an appropriate amount of antioxidants. The copolymer is imported from abroad, and purchased from ExxonMobil 3518GA.

Example 13

[0072] Example 13 provides pipes of the thermoplastic crosslinked polyethylene material, which was prepared by subjecting the thermoplastic crosslinked polyethylene particles in the example 1 of the application to screen to select particles having a particle diameter of 23 mm. The pipes of the thermoplastic crosslinked polyethylene material were prepared using ordinary HDPE pipe or PERT pipe manufacturing equipment. The pipes should be connected by socket welding, and the waste products can be made into the pipes of the thermoplastic crosslinked polyethylene after being crushed and granulated. The pipes obtained in this example can be used for a hot water system, a drinking water system, a wear resistant, heat resistant and corrosion resistant oil extracting lined pipe, and a working pipe of heat pipeline, etc.

Example 14

[0073] Example 14 provides a conveyor idler of the thermoplastic crosslinked polyethylene material, which was prepared by subjecting the thermoplastic crosslinked polyethylene particles in the example 5 of the application to screen to select particles having a particle diameter of 23 mm, and injection-molding by an injection molding machine to obtain the conveyor idler of the thermoplastic crosslinked polyethylene material, which has properties of wear resistant and corrosion resistant, and can be widely applied to belt conveyors in places such as a salt field or a mine.

Example 15

[0074] Example 15 provides a hollow article of the thermoplastic crosslinked polyethylene material, which was prepared by subjecting the thermoplastic crosslinked polyethylene particles in the example 1 of the application to screen to select particles having a particle diameter of 23 mm, and blow molding by a polyethylene hollow container molding machine to obtain a plastic barrel of 58 L.

Example 16

[0075] Example 16 provides a rotational molding product of the thermoplastic crosslinked polyethylene material, which was prepared by subjecting the thermoplastic crosslinked polyethylene particles in the example 1 of the application to screen to select particles having a particle diameter of 0.20.25 mm, and rotational molding by a rotational molding machine to obtain the rotational molding product of the thermoplastic crosslinked polyethylene material, which has properties of abrasion resistant, heat resistant, corrosion resistant, and high impact resistant.

Comparative Example 1

[0076] Comparative Example 1 provides a hose of polyethylene material, which was prepared by the method of Example 1 in the Chinese patent document CN102875877A.

Comparative Example 2

[0077] Comparative Example 2 provides a pipe of polyethylene material, which was prepared by the same method as in Example 13. The difference of Comparative Example 2 from Example 13 is that high density polyethylene (HDPE) in the raw material of the polyethylene material used in the Comparative Example 2 contains a certain antioxidant, and is purchased from Sinopec Qilu Petrochemical Company.

Experimental Example 1

[0078] A hydrostatic test direct to the thermoplastic crosslinked polyethylene pipes of Example 13 was carried out in accordance with the provisions of GB/T18992.2-2003 Crosslinked polyethylene (PE-X) piping system for hot and cold water (Part 2: Pipes). The test results were shown in Table 1 below.

TABLE-US-00001 TABLE 1 Hydrostatic test results of thermoplastic crosslinked polyethylene pipes Test temperature/ Hydrostatic Test Whether it has permeation or C. stress/MPa time/h failure? 20 12 1 no permeation and no failure 95 4.8 1 no permeation and no failure 95 4.7 22 no permeation and no failure 95 4.6 165 no permeation and no failure 95 4.4 1000 no permeation and no failure

Experimental Example 2

[0079] Performance tests of Example 13, Comparative Example 1, Comparative Example 2, commercially available PE-RTII pipes and commercially available PE-Xa pipes were carried out. The test results were shown in Table 2 below.

TABLE-US-00002 TABLE 2 Performance test results of various pipes Commercially available Commercially Example Comparative Comparative PE-RTII available Items 13 Example 1 Example 2 pipes PE-Xa pipes MFR (190 C., 1.35 g/10 min 0.6 g/10 min 21.6 kg weight) Degree of 0.7~1.3 20~35 70~90 crosslinking/% Vicat softening 126.1 120.1 126.9 121.9 127.3 point/ C. 20 C. tensile 7.93e0.3 15.24e0.3 11.47e0.3 13.83e0.3 10.28e0.3 creep/% 95 C. tensile 26.37e0.3 24.56e0.3 12.02e0.3 creep/% 110 C. tensile 17.33e0.3 32.21e0.3 23.32e0.3 28.79e0.3 18.76e0.3 creep/% 30 C. 100% 17.74 14.03 17.65 14.58 17.74 tensile modulus/MPa 70 C. 100% 10.96 7.17 10.13 8.92 10.96 tensile modulus/MPa 95 C. 100% 8.03 4.91 7.16 5.72 6.34 tensile modulus/MPa 110 C. 100% 5.35 3.26 5.17 4.18 5.07 tensile modulus/MPa bending 13.03 10.4 12.87 10.54 12.72 strength/MPa bending 424 247 451 415 527 modulus/MPa Impact strength/ 89.89 71.2 93.32 88.08 105.12 KJ/m2

[0080] In table 2, MFR represents the mass flow rate of solution, the test method of which refers to GB/T 3682-2000 (IS01133); Vicat softening point refers to the temperature at which a polymer sample is pressed into a depth of 1 mm by 1 mm.sup.2 pin in the liquid heat transfer medium at a certain load and a certain constant speed heating condition. The test method of which refers to GB/T1633 Measurement of Thermoplastic Softening Temperature (VST); The test method of tensile creep refers to GB/T11546.1-2008 (150899-1:2003).

[0081] It is apparent that the above-described examples are merely examples for clearly illustrating the present application, and are not intended to limit the present application. Based on the above description, other variations or modifications of various forms may be made by one skilled in the art. Here, there is no need and no way to exhaust all examples. The obvious variations or modifications which are derived therefrom are still within the scope of the application.