A polyolefin material, its preparation and use

Abstract

The present application relates to a kind of polyolefin materials and its preparation method and application.The polyolefin material includes the following weight parts of components: polyethylene 10-20 parts, polyolefin elastomer 10-30 parts, inorganic filler 40-60 parts, hyperbranched polyester 3.5-9 parts.The polyolefin material of the present application has good gloss, good scratch resistance and good processing performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer material modification, and more particularly to a polyolefin material and a preparation method and application thereof. BACKGROUND

[0002] With the world's emphasis on environmental protection, the trend of low-smoke halogen-free cable replacing traditional PVC cable is becoming more and more obvious; in order to meet the performance requirements, low-smoke halogen-free cable generally adopts PE / EVA / POE / filler formula system, but the surface gloss and scratch resistance of such high-filled and multi-resin alloy system after extrusion cannot reach the level of PVC cable. The annual demand of low-smoke halogen-free cable material market is about 800,000 tons, and the products are mainly used in home decoration and engineering building cloth wires, photovoltaic wires, automobile wires, power cables, communication cables, internal connecting wires of electrical appliances, optical fiber cables, etc., which basically require good gloss and scratch resistance, especially for photovoltaic wires and automobile wires for export, long-distance transportation, and surface scratch resistance is particularly important.

[0003] In order to meet the above strict requirements, many domestic and foreign manufacturers currently use PEEK material as cable sheath material, but this material is extremely expensive and requires special equipment for extrusion, which is extremely inconvenient to process. In addition, some manufacturers add polyvinylidene fluoride (PVDF) or ultra-high molecular weight polyethylene (UHMWPE) to the existing formula system to improve the wear resistance of the composite material for cables, but due to the significant difference in melting point with the low-smoke halogen-free formula system, the effect of improving the scratch resistance of the finished cable is limited, and excessive addition may cause poor plasticization during extrusion.

[0004] Therefore, it is necessary to solve the problems of poor scratch resistance, low gloss or poor processing performance of the current cable material. SUMMARY

[0005] The primary object of the present application is to overcome the problems of poor scratch resistance, low gloss or poor processing performance of the existing cable material, and to provide a polyolefin material.

[0006] A further object of the present application is to provide a preparation method of the above-mentioned polyolefin material.

[0007] A further object of the present application is to provide the application of the above-mentioned polyolefin material in the preparation of cables.

[0008] The above objects of the present application are achieved by the following technical solutions:

[0009] A polyolefin material, comprising the following components in parts by weight:

[0010] polyethylene 10-20 parts,

[0011] polyolefin elastomer 10-30 parts,

[0012] inorganic filler 40-60 parts,

[0013] hyperbranched polyester 3.5-9 parts;

[0014] the content of amide groups in the hyperbranched polyester is 5-10 wt%.

[0015] The inventor of the present application found that, by adding the hyperbranched polyester with a specific content of amide groups to the polyethylene / polyolefin elastomer / inorganic filler system, the polyester segments of the hyperbranched polyester have good compatibility with the formulation system of the present application, and the amide groups of the hyperbranched polyester form a dense lubricating layer by being distributed on the surface of the polyolefin material, thereby improving the scratch resistance of the polyolefin material, and the lubricating layer is also conducive to improving the gloss of the polyolefin material. In addition, the hyperbranched polyester itself can also play a lubricating role, improving the dispersibility and compatibility of the components during material processing, thereby improving the gloss and processing performance of the polyolefin material.

[0016] In the present application, preferably, the content of polyethylene in the polyolefin material is at least 8 wt%.

[0017] Preferably, the melt index of the polyethylene under the test conditions of 190℃ and 2.16Kg is 1-7g / 10min.

[0018] In the present application, the melt index of the polyethylene can be measured according to GB / T 3682-2000.

[0019] Preferably, the polyolefin elastomer is at least one of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer or ethylene-butyl acrylate copolymer.

[0020] Preferably, the melt index of the polyolefin elastomer under the test conditions of 190℃ and 2.16Kg is 0.5-10g / 10min.

[0021] In the present application, the melt index of the polyolefin elastomer can be measured according to GB / T 3682-2000.

[0022] Preferably, the inorganic filler is a flame-retardant inorganic filler.

[0023] More preferably, the flame-retardant inorganic filler is at least one of aluminum hydroxide or magnesium hydroxide.

[0024] Preferably, the particle size D50 of the inorganic filler is 0.1-5μm. The particle size D50 of the inorganic filler can be measured by a particle size analyzer.

[0025] In the present application, the amide groups of the hyperbranched polyester are end capping groups.

[0026] In the present application, the content of the amide groups of the hyperbranched polyester refers to the mass percentage of CO-NH in the hyperbranched polyester. The content of the amide groups of the hyperbranched polyester can be measured by elemental analysis, specifically: first, the N element content of the hyperbranched polyester is measured by an elemental analyzer, and then the N element content is converted into the content of the amide groups.

[0027] In the present application, the hyperbranched polyester is capped by a capping agent and a carboxyl-terminated hyperbranched polyester, and the carboxyl-terminated hyperbranched polyester is obtained by copolymerization of a trihydric alcohol and a diacid; preferably, the capping agent includes but is not limited to methylamine, the trihydric alcohol includes but is not limited to glycerol, and the diacid includes but is not limited to oxalic acid.

[0028] The preparation process of the hyperbranched polyester of the present application is as follows: 40-80 parts by weight of a trihydric alcohol and 90-130 parts by weight of a diacid are mixed and subjected to a polymerization reaction for 3-5 hours, and then methylamine is introduced for 4-6 min, to obtain the hyperbranched polyester; the introduction rate of the methylamine is 0.06-0.12 mL / min.

[0029] Specifically, the polymerization reaction is carried out at 100-130℃; the polymerization reaction is carried out in the presence of a catalyst, and the catalyst includes but is not limited to n-butyl titanate.

[0030] Preferably, the melting point of the hyperbranched polyester is 40-70℃.

[0031] More preferably, the melting point of the hyperbranched polyester is 60-65℃. The hyperbranched polyester with the melting point in this range has higher gloss, better scratch resistance and better processing performance.

[0032] In the present application, the content of the amide groups of the hyperbranched polyester can be specifically 5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt%.

[0033] Preferably, the content of the amide groups of the hyperbranched polyester is 7.4-9wt%. The hyperbranched polyester with the content of the amide groups in this range has higher gloss, better scratch resistance and better processing performance.

[0034] Preferably, the polyolefin material further comprises 0.5-2 parts of other auxiliary agents.

[0035] More preferably, the other auxiliary agent is at least one of an antioxidant or a lubricating aid.

[0036] Further preferably, the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant DSTDP, or antioxidant 1076.

[0037] Further preferably, the lubrication aid is at least one of silicone masterbatch, silicone oil, or PE wax.

[0038] The polyolefin material is prepared by mixing the components, melt extruding, and granulating.

[0039] Preferably, the melt extrusion temperature is 130-150℃, the screw length-diameter ratio of the extruder is 35-45:1, and the screw rotation speed is 400-500r / min.

[0040] The polyolefin material is prepared by mixing the components, melt extruding, and granulating.

[0041] Compared with the prior art, the polyolefin material has the following advantages:

[0042] The polyolefin material has good gloss, good scratch resistance, and good processing performance. DETAILED DESCRIPTION

[0043] In order to more clearly and completely describe the technical solutions of the present application, the present application is further described in detail below through specific examples, which should be understood as merely illustrating the present application, and not limiting the present application, and various changes can be made within the scope of the present application.

[0044] Some reagents used in the examples and comparative examples of the present application are described as follows:

[0045] Polyethylene 1#: melt index under the test conditions of 190℃ and 2.16Kg is 6g / 10min, brand LLDPE 7150, manufacturer Qilu Petrochemical;

[0046] Polyethylene 2#: melt index under the test conditions of 190℃ and 2.16Kg is 1.9g / 10min, brand LDPE 2420H, manufacturer Zhonghai Shell;

[0047] Polyolefin elastomer 1#: EVA, melt index under the test conditions of 190℃ and 2.16Kg is 1g / 10min, EVA00320, Yangzi Petrochemical;

[0048] Polyolefin elastomer 2#: POE, melt index under the test conditions of 190℃ and 2.16Kg is 1.2g / 10min, POE LC168, LG Chemical;

[0049] Inorganic filler 1#: magnesium hydroxide, particle size D50 = 0.1 μm, MDH-1, Yingkou, Liaoning;

[0050] Inorganic filler 2#: magnesium hydroxide, particle size D50 = 3 μm, MDH-2, Yingkou, Liaoning;

[0051] Inorganic filler 3#: aluminum hydroxide, particle size D50 = 4 μm, ATH-1, Zhongal Group;

[0052] Other auxiliary agent 1#: antioxidant 1010, commercially available;

[0053] Hyperbranched polyester 1#: self-made, the preparation process is as follows: 60 parts by weight of glycerol, 110 parts by weight of oxalic acid, 0.5% of n-butyl titanate based on the total mass of acid and alcohol are added into a reaction kettle, after reaction at 120°C for 4 hours (denoted as time t), 5 min of methylamine is introduced at a rate of 0.1 mL / min; the water produced in the reaction is removed, and the reaction product is obtained after cooling to room temperature. The obtained reaction product is dried by vacuum extraction for 2 hours to obtain the hyperbranched polyester; the content of amide groups of the hyperbranched polyester 1# is 7.5 wt%, and the melting point is 60°C.

[0054] Hyperbranched polyester 2#: self-made, which is different from the hyperbranched polyester 1# in that the rate of methylamine introduction is 0.06 mL / min. The content of amide groups of the hyperbranched polyester 2# is 6 wt%, and the melting point is 60°C.

[0055] Hyperbranched polyester 3#: self-made, which is different from the hyperbranched polyester 1# in that the rate of methylamine introduction is 0.12 mL / min. The content of amide groups of the hyperbranched polyester 3# is 8.5 wt%, and the melting point is 60°C.

[0056] Hyperbranched polyester 4#: self-made, which is different from the hyperbranched polyester 1# in that the reaction time t is 3 hours. The content of amide groups of the hyperbranched polyester 4# is 7.4 wt%, and the melting point is 45°C.

[0057] Hyperbranched polyester 5#: self-made, which is different from the hyperbranched polyester 1# in that the reaction time t is 5 hours. The content of amide groups of the hyperbranched polyester 5# is 7.7 wt%, and the melting point is 65°C.

[0058] Hyperbranched polyester 6#: self-made, which is different from the hyperbranched polyester 1# in that the rate of methylamine introduction is 0.03 mL / min. The content of amide groups of the hyperbranched polyester 6# is 3 wt%, and the melting point is 60°C.

[0059] Hyperbranched polyester 7#: self-made, which is different from the hyperbranched polyester 1# in that no methylamine is introduced. The hyperbranched polyester 7# does not contain amide groups, and the melting point is 60°C.

[0060] Non-hyperbranched polyester 8#: self-made, different from hyperbranched polyester 1# in that 60 parts by weight of ethylene glycol and 110 parts by weight of oxalic acid are added. The content of amide groups of non-hyperbranched polyester 8# is 2wt%, and the melting point is 55℃.

[0061] Hyperbranched polyester 9: vinyl-terminated hyperbranched polyester, self-made, different from hyperbranched polyester 1# in that propylene alcohol is used instead of methylamine to prepare the vinyl-terminated hyperbranched polyester. The vinyl content of hyperbranched polyester 9 is 7.4wt%, and the melting point is 59℃.

[0062] Hyperbranched polyesteramide: HyPer N101, Wuhan Hyperbranched Resin Technology Co., Ltd.

[0063] Unless otherwise specified, each component (such as other auxiliary agent 1#) selected in each parallel example and comparative example is the same commercially available product.

[0064] The polyolefin material provided by each embodiment and comparative example of the present application is subjected to performance determination according to the following test method:

[0065] (1) Gloss: The double-roller open mill is heated to 120℃, and after the temperature is stable, the material is placed in the double-roller open mill for mixing for about 5 minutes, then the sheet is taken out, and then the sheet is preheated for 5 minutes without pressure and heated and pressurized for 5 minutes in a flat bed fluidizer at a temperature of 180℃, and then the sheet is pressurized and cooled to room temperature to be taken out of the mold, and the pressure is set to 13MPa. The 1mm-thick test sheet taken out of the mold should be smooth and clean, uniform in thickness, and free of bubbles. The gloss is tested by a non-contact gloss meter YG60L.

[0066] (2) Scratch resistance: The double-roller open mill is heated to 120℃, and after the temperature is stable, the material is placed in the double-roller open mill for mixing for about 5 minutes, then the sheet is taken out, and then the sheet is preheated for 5 minutes without pressure and heated and pressurized for 5 minutes in a flat bed fluidizer at a temperature of 180℃, and then the sheet is pressurized and cooled to room temperature to be taken out of the mold, and the pressure is set to 13MPa. The 1mm-thick test sheet taken out of the mold should be smooth and clean, uniform in thickness, and free of bubbles. The scratch resistance is tested by a cross scratch tester, and the scratch resistance is represented by the scratch depth. The smaller the scratch depth, the better the scratch resistance.

[0067] (3) Processability: The maximum linear speed that can be achieved during extrusion is used to represent the processability, and the standard for judgment is that the finished product line does not have diameter fluctuations and the surface does not have appearance defects at this maximum linear speed.

[0068] The polyolefin material provided by each embodiment and comparative example of the present application is prepared according to the following method:

[0069] The components are weighed according to the formula, then added to a twin-screw extruder from the main feeder, melt-extruded, and granulated to obtain the polyolefin material; wherein the length-diameter ratio of the screw of the twin-screw extruder is 40:1; the screw rotation speed is 350 r / min, and the melt temperature is 130-150℃.

[0070] Examples 1-13

[0071] Examples 1-13 provide a series of polyolefin materials, whose formula is shown in Table 1.

[0072] Table 1 Formula of Examples 1-13 (parts by weight)

[0073]

[0074] Comparative Examples 1-7

[0075] Comparative Examples 1-7 provide a series of polyolefin materials, which are prepared by the same method as Example 1, and whose formula is shown in Table 2.

[0076] Table 2 Formula of Comparative Examples 1-7 (parts by weight)

[0077]

[0078]

[0079] The properties of the polyolefin materials of each example and comparative example are determined according to the above-mentioned test methods, and the test results are shown in Table 3.

[0080] Table 3 Property results of each example and comparative example

[0081]

[0082]

[0083] From Table 3, it can be seen that:

[0084] The glossiness of the polyolefin materials of Examples 1-13 is all above 90, the scratch depth of the scratch resistance test is all below 30 μm, and the maximum linear speed in the processing performance test is all above 150 m / min, indicating that the polyolefin materials of the present application have good glossiness, good scratch resistance, and good processing performance.

[0085] Comparative Example 1 is added with isophthalic acid amide, the glossiness of the obtained polyolefin material is low, the scratch resistance cannot be improved well, and the processing performance is poor. Comparative Example 2 is added with hyperbranched polyester with too low amide group content, the glossiness of the obtained polyolefin material is poor, and the scratch resistance cannot be improved well. Comparative Example 3 is added with hyperbranched polyester without amide group, the glossiness of the obtained polyolefin material is poor, and the scratch resistance cannot be improved well. Comparative Example 4 is added with non-hyperbranched polyester, the performance of the obtained polyolefin material is similar to that of Comparative Example 1. Comparative Example 5 is not added with hyperbranched polyester, and the performance of the obtained polyolefin material is poor. Comparative Example 6 is added with hyperbranched polyester containing vinyl group, the glossiness of the obtained polyolefin material is low, and the scratch resistance cannot be improved well. Comparative Example 7 is added with hyperbranched polyamide, and the performance of the obtained polyolefin material is poor.

[0086] Obviously, the above embodiments of the present application are merely exemplary and are not intended to limit the embodiments of the present application. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. All the embodiments are not required to be enumerated. Any modification, equivalent replacement and improvement within the spirit and principle of the present application shall be included in the protection scope of the claims of the present application.

Claims

1. A polyolefin material, characterized in that, The polyolefin material comprises the following components in parts by weight: polyethylene 10-20 parts, polyolefin elastomer 10-30 parts, inorganic filler 40-60 parts, hyperbranched polyester 3.5-9 parts; the content of amide groups in the hyperbranched polyester is 5-10 wt%; the amide groups in the hyperbranched polyester are end-capping groups; the hyperbranched polyester is end-capped by an end-capping agent and a carboxyl-terminated hyperbranched polyester, the carboxyl-terminated hyperbranched polyester is obtained by copolymerization of a trihydric alcohol and a diacid; the melting point of the hyperbranched polyester is 40-70℃; the melt index of the polyethylene under the test conditions of 190℃ and 2.16 Kg is 1-7 g / 10 min; the polyolefin elastomer is at least one of ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer or POE.

2. The polyolefin material according to claim 1, characterized in that, The inorganic filler is a flame-retardant inorganic filler.

3. The polyolefin material of claim 1, wherein, The particle size D50 of the inorganic filler is 0.1-5 μm.

4. The polyolefin material of claim 1, wherein, The content of amide groups in the hyperbranched polyester is 7.4-9 wt%.

5. The polyolefin material of claim 1, wherein, The polyolefin material further comprises other auxiliary agents 0.5-2 parts.

6. Process for the production of a polyolefin material according to any one of claims 1 to 5, characterized in that, The polyolefin material is prepared by mixing the components, melt extruding and granulating.

7. Use of the polyolefin material according to any one of claims 1-5 in the preparation of a cable.

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