A low-smoke halogen-free polyolefin composition for waterborne photovoltaics and a preparation method and application thereof

Abstract

The application discloses a low-smoke halogen-free polyolefin composition for water photovoltaics, and a preparation method and application thereof. The polyolefin composition comprises the following components in parts by weight: 15-90 parts of polyolefin resin; 3-10 parts of polyolefin grafted maleic anhydride; 50-100 parts of halogen-free flame retardant; 0.3-2 parts of coupling agent; 0.3-1 part of amphiphilic surfactant; and 0.5-2 parts of crosslinking aid. The polyolefin resin has a vinyl acetate content of 14wt%-26wt%, and the amphiphilic surfactant has a hydroxyl value of 25-60mgKOH / g. The polyolefin composition has good water breakdown resistance, and is especially suitable for water photovoltaic cable sheath material.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of cable materials, and particularly relates to a low-smoke halogen-free polyolefin composition for water photovoltaics, and a preparation method and application thereof. BACKGROUND

[0002] With the increasing development speed of photovoltaics, the application mode of photovoltaic power generation presents a multi-field and diversified development trend, and at present, large land photovoltaic power generation projects are gradually saturated, and there are a large number of places for installing floating photovoltaics in vast lakes, rivers and oceans.

[0003] However, water photovoltaics need to be soaked in water for a long time or be in a humid environment for a long time, and the application environment is harsh; according to the requirements of photovoltaic cable standards, low-smoke halogen-free requirements need to be met, so that the flame retardant is mainly aluminum hydroxide or magnesium hydroxide, but it is very easy to absorb water and moisture, resulting in poor water breakdown resistance, which limits its application. Therefore, the application provides a low-smoke halogen-free polyolefin composition for water photovoltaics, which has good water breakdown resistance and can meet the needs of use in a long-term humid environment, ensuring the safety of the cable. SUMMARY

[0004] The purpose of the present application is to overcome the poor water breakdown resistance of the low-smoke halogen-free polyolefin material in the prior art, and to provide a low-smoke halogen-free polyolefin composition for water photovoltaics.

[0005] Another purpose of the present application is to provide a preparation method of the low-smoke halogen-free polyolefin composition for water photovoltaics.

[0006] Another purpose of the present application is to provide an application of the low-smoke halogen-free polyolefin composition for water photovoltaics.

[0007] To achieve the above-mentioned purposes, the present application adopts the following technical solutions:

[0008] A low-smoke halogen-free polyolefin composition for water photovoltaics comprises the following components calculated by weight parts:

[0009]

[0010] The content of vinyl acetate in the polyolefin resin is 14wt%-26wt%, and the hydroxyl value of the amphiphilic surfactant is 25-60mgKOH / g.

[0011] In the present application, by selecting polyolefin resin as the base resin, adjusting the content of vinyl acetate in the base resin to 14wt%-26wt%, the material surface polarity can be ensured, adding amphiphilic surfactant and adjusting its hydroxyl value, the polar groups can be close to the resin layer, the non-polar segment is outside, the surface free energy of the material is reduced; the compatibility of halogen-free flame retardant and polyolefin resin is improved by using coupling agent, the interface is more firm, can resist the infiltration of water molecules, so that the material shows good hydrophobic property, thereby having good water breakdown resistance.

[0012] It should be noted that the water-based photovoltaic low-smoke halogen-free polyolefin composition in the present application, the content of the polyolefin resin in the base resin is preferably not less than 50wt%.

[0013] It should be noted that the content of vinyl acetate in the polyolefin resin in the present application is 14wt%-26wt%, for example but not limited to 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt%, 21wt%, 22wt%, 23wt%, 24wt%, 25wt% or 26wt% and specific point values between the above point values, limited to the length and for the sake of simplicity, the specific point values included in the range are not listed in the present application.

[0014] Further, the content of vinyl acetate in the polyolefin resin is 15-25wt%.

[0015] Further, the content of vinyl acetate in the polyolefin resin is 18-22wt%. In this range, it is easier to attract amphiphilic surfactant, so that the non-polar end is outside, and the water breakdown resistance of the polyolefin composition is better.

[0016] Specifically, the content of vinyl acetate in the polyolefin resin is =(weight of ethylene-vinyl acetate x content of vinyl acetate) / total weight of polyolefin resin.

[0017] Specifically, the content of vinyl acetate in the ethylene-vinyl acetate is determined by infrared spectroscopy method in GB / T 30925-2014.

[0018] It should be noted that the hydroxyl value of the amphiphilic surfactant in the present application is 25-60mgKOH / g, for example but not limited to 25mgKOH / g, 30mgKOH / g, 35mgKOH / g, 40mgKOH / g, 45mgKOH / g, 50mgKOH / g, 55mgKOH / g or 60mgKOH / g and specific point values between the above point values, limited to the length and for the sake of simplicity, the specific point values included in the range are not listed in the present application.

[0019] Further, the hydroxyl value of the amphiphilic surfactant is 30-55 mgKOH / g.

[0020] Further, the hydroxyl value of the amphiphilic surfactant is 30-55 mgKOH / g.

[0021] Specifically, the hydroxyl value is determined according to GB / T 7383-2020 Method A (phthalic anhydride method).

[0022] Further, the amphiphilic surfactant comprises one or more of ethoxylated amide wax, polyoxyethylene ether or polyethylene glycol.

[0023] Further, the amphiphilic surfactant comprises one or more of ethoxylated amide wax, polyoxyethylene ether or polyethylene glycol.

[0024] It should be noted that the amphiphilic surfactant in the present application is 0.5-1 parts, for example, but not limited to 0.5 parts, 0.55 parts, 0.6 parts, 0.65 parts, 0.7 parts, 0.75 parts, 0.8 parts, 0.85 parts, 0.9 parts, 0.95 parts or 1 part, etc. can achieve the present application.

[0025] It should be noted that the polyolefin resin in the present application, those skilled in the art can select the commonly used polyolefin resin as the base resin according to the prior art. For example, but not limited to, the polyolefin resin comprises 0-25 parts of polyethylene, 15-40 parts of ethylene-vinyl acetate, 0-25 parts of POE. Under this amount, it is especially suitable for low smoke halogen-free flame retardant photovoltaic cable material.

[0026] Further, the melt flow rate of the polyolefin resin under a load of 2.16 kg at 190℃ is 0.5-8 g / 10 min.

[0027] Specifically, the test standard of the melt flow rate is GB / T 3682-2000.

[0028] Further, the coupling agent comprises a silane coupling agent and / or a titanate coupling agent.

[0029] Specifically, the silane coupling agent comprises one or more of amino silane, epoxy silane, and methacryloyloxy silane.

[0030] The titanate coupling agent comprises pyrophosphate titanate and / or di(octylphosphate) titanate di(glycolate).

[0031] Further, the crosslinking coagent is one or more of triallyl isocyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate.

[0032] Further, the halogen-free flame retardant is a hydroxide flame retardant.

[0033] Further, the hydroxide flame retardant is magnesium hydroxide and / or aluminum hydroxide.

[0034] Further, the polyolefin grafted maleic anhydride is POE grafted maleic anhydride and / or PE grafted maleic anhydride.

[0035] Specifically, the maleic anhydride grafting rate of the polyolefin grafted maleic anhydride is 0.5-2wt%.

[0036] Specifically, the testing method of the maleic anhydride grafting rate is acid-base titration method.

[0037] Further, the low smoke halogen-free polyolefin composition for waterborne photovoltaic further comprises 0.5-2.5 parts of calcium silicate. The addition of calcium silicate can further improve the water impact resistance of the prepared polyolefin composition.

[0038] Further, the low smoke halogen-free polyolefin composition for waterborne photovoltaic further comprises 0.1-5 parts of an auxiliary agent.

[0039] Specifically, the auxiliary agent, for example but not limited to, comprises one or more of an antioxidant, a lubricant, a weathering agent or a toner.

[0040] In the present application, a commonly used antioxidant can be selected, for example but not limited to, one or more of a hindered phenolic antioxidant, a phosphite antioxidant or a thioester antioxidant.

[0041] Specifically, the hindered phenolic antioxidant is one or more of N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyphenylpropionamide) (Irganox 1098), pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 1010), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (Antioxidant 1790), 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox 259), n-octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (Irganox 1076) or 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acrylate]-1,1-dimethyl}-2,4,8,10-tetraoxaspiro[undecane] (ADK AO-80).

[0042] The phosphite antioxidant is one or several of tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite (PEP-36) or Irgafos® 627A.

[0043] The thioester antioxidant is one or several of distearyl thiodipropionate, didodecyl thiodipropionate (antioxidant DLTDP), dilauryl thiodipropionate or pentaerythritol dithiopropionate.

[0044] The present application can select the commonly used lubricants, such as but not limited to one or several of vinyl bis stearamide, polysiloxane, calcium stearate, magnesium stearate, zinc stearate, silicone, PE wax, or PP wax.

[0045] In the present application, the commonly used weathering agent can be selected according to the prior art, such as but not limited to hindered amine light stabilizer and benzotriazole ultraviolet light absorber.

[0046] Specifically, the hindered amine light stabilizer is 2,2,6,6-tetramethyl-4-piperidinyl stearate and / or bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0047] Further, the low-smoke halogen-free polyolefin composition for waterborne photovoltaic includes the following components according to weight parts:

[0048]

[0049] The present application also protects the preparation method of the above-mentioned low-smoke halogen-free polyolefin composition for waterborne photovoltaic, which includes the following steps:

[0050] The components are mixed uniformly in proportion through the internal mixer, extruded and granulated through the extruder, and cooled to obtain.

[0051] Specifically, the temperature of the internal mixer is 140-160℃.

[0052] In some specific embodiments, after the components are mixed uniformly in proportion through the internal mixer, they are added into the twin-screw extruder through the feeding port, the length-diameter ratio is 40:1, the rotation speed is 300-400 rpm, the temperature is 100-140℃, and then they pass through the single-screw extruder, the temperature is 100-140℃, and air-cooled die granulation and cooling are performed to obtain.

[0053] The present application also protects the application of the above-mentioned low-smoke halogen-free polyolefin composition for waterborne photovoltaic in the preparation of waterborne photovoltaic cable sheath material.

[0054] Compared with the prior art, the present application has the following beneficial effects:

[0055] The application provides a low-smoke halogen-free polyolefin composition for waterborne photovoltaics, which is prepared by using a polyolefin resin as a base resin, adding an amphiphilic surfactant, and adjusting the content of vinyl acetate in the base resin, so that the hydrophobicity of the polyolefin composition is improved by the synergistic effect of the coupling agent, the polyolefin composition has good water breakdown resistance, and is especially suitable for waterborne photovoltaic sheath materials. DETAILED DESCRIPTION

[0056] The application will be further described in detail below with specific examples, which are used to explain the application and are not used to limit the scope of the application. In the following examples, the test methods are conventional methods unless otherwise specified, and the materials, reagents, etc. are commercially available unless otherwise specified.

[0057] 1. Raw materials used in each example and comparative example:

[0058] Polyolefin resin:

[0059] Polyethylene (PE): LLDPE 3812PA, purchased from Exxon Mobil;

[0060] Ethylene-vinyl acetate copolymer (EVA):

[0061] EVA1: EVA 7350M, VA content 18 wt%, purchased from Taiwan Plastics Industry Co., Ltd.;

[0062] EVA2: EVA V6110MC, VA content 28 wt%, purchased from Yangzi Petrochemical-BASF Co., Ltd.;

[0063] EVA3: ELVAX 40L-03, VA content 40 wt%, purchased from DuPont, USA;

[0064] POE: POE 58750, purchased from Dow Chemical;

[0065] Halogen-free flame retardant: aluminum hydroxide, AH-01DG, purchased from Luoyang Zhongchao New Material Co., Ltd.;

[0066] Coupling agent: aminosilane, KH-550, purchased from Anhui Sibao Organic Silicon New Material Co., Ltd.;

[0067] Amphiphilic surfactant:

[0068] Amphiphilic surfactant 1: polyoxyethylene ether, UNITHOX 750, hydroxyl value 33 mgKOH / g, purchased from Nucera Solutions;

[0069] Amphiphilic surfactant 2: polyoxyethylene ether, UNITHOX 550, hydroxyl value of 41 mg KOH / g, purchased from Nucera Solutions;

[0070] Amphiphilic surfactant 3: polyoxyethylene ether, UNITHOX 720, hydroxyl value of 52 mg KOH / g, purchased from Nucera Solutions;

[0071] Amphiphilic surfactant 4: polyoxyethylene ether, UNITHOX 450, hydroxyl value of 55 mg KOH / g, purchased from Nucera Solutions;

[0072] Amphiphilic surfactant 5: polyethylene glycol, PEG-3350, hydroxyl value of 34 mg KOH / g, purchased from Dow Chemical;

[0073] Amphiphilic surfactant 6: polyoxyethylene ether, UNITHOX 480, hydroxyl value of 22 mg KOH / g, purchased from Nucera Solutions;

[0074] Amphiphilic surfactant 7: polyoxyethylene ether, UNITHOX 420, hydroxyl value of 85 mg KOH / g, purchased from Nucera Solutions;

[0075] Amphiphilic surfactant 8: polyethylene glycol, PEG-8000, hydroxyl value of 13 mg KOH / g, purchased from Dow Chemical;

[0076] Calcium silicate: purchased from Inner Mongolia Datang International Renewable Resources Co., Ltd.;

[0077] Calcium carbonate: CC-800, purchased from Jiangxi Guangyuan Chemical Industry;

[0078] Polyolefin grafted maleic anhydride: POE grafted maleic anhydride, N423, purchased from Ningbo Nengzhiguang New Material;

[0079] Crosslinking coagent: triallyl isocyanurate, commercially available;

[0080] Antioxidant: a compound of antioxidant 1790, antioxidant 168 and antioxidant DLTDP in a mass ratio of 3:1:2, all commercially available; it should be noted that the same raw materials were used in the parallel experiments of the examples and comparative examples of the present application.

[0081] 2. The polyolefin compositions described in each example and comparative example were prepared according to the formulations in Tables 1-2 by the following method:

[0082] The components were mixed uniformly in a proportion through a Banbury mixer at 150℃, added into a twin-screw extruder through a feeding port, the length-diameter ratio was 40:1, the rotating speed was 350 rpm, the temperature was 120℃, then passed through a single-screw extruder, the temperature was 120℃, and then granulated by air-cooling die face, and cooled to obtain.

[0083] 3. Performance test

[0084] The polyolefin compositions prepared in each example and comparative example were extruded into 4mm 2 The cable was subjected to pressure resistance test, the pressure resistance test was tested according to the standard 2PFG 2750 / 09.20, and the requirement ≥2016h was met.

[0085] Examples 1-12 and Comparative Examples 1-6

[0086] Table 1: The amount of each component (unit: weight parts) and performance of the low-smoke halogen-free polyolefin composition for waterborne photovoltaic in examples 1-12

[0087]

[0088]

[0089]

[0090] Table 2: The amount of each component (unit: weight parts) and performance of the polyolefin composition in comparative examples 1-6

[0091] Comparative Example 1 2 3 4 5 6 PE 5 5 5 / 5 5 EVA1 / / / / / / EVA2 / / / / 15 / EVA3 20 20 20 30 / 20 POE 15 15 15 10 20 15 Polyolefin grafted maleic anhydride 5 5 5 5 5 5 Halogen-free flame retardant 60 60 60 60 60 60 Coupling agent 0.5 0.5 0.5 0.5 0.5 / Amphiphilic surfactant 1 / / / 0.5 0.5 0.5 Amphiphilic surfactant 6 0.5 / / / / / Amphiphilic surfactant 7 / 0.5 / / / / Amphiphilic surfactant 8 / / 0.5 / / / Crosslinking coagent 1 1 1 1 1 1 Antioxidant 1 1 1 1 1 1 VA content in polyolefin resin (wt%) 20 20 20 30 10.5 20 Breakdown time (h) 1853 1984 1766 1962 1976 1928

[0092] As can be seen from Table 1, the low-smoke halogen-free polyolefin composition for waterborne photovoltaic prepared by the application has good water breakdown resistance, specifically, the water breakdown resistance time is not less than 2016h, meeting the standard 2PFG 2750 / 09.20; further preferably, the water breakdown resistance time is not less than 2200h.

[0093] As can be seen from the comparison of comparative examples 1-3 and examples 2, 5-8, if the hydroxyl value of the amphiphilic surfactant selected is too low or too high, the water breakdown resistance time will decrease significantly; this may be due to the fact that when the hydroxyl value is too low, the polar groups in the polyolefin resin cannot be close to the resin layer, and the non-polar segments are on the outside, resulting in a decrease in breakdown time; when the hydroxyl value is too high, there are more hydroxyl groups exposed on the surface, so that water easily enters the polyolefin composition, resulting in a decrease in water breakdown resistance.

[0094] As can be seen from the comparison of Comparative Examples 4-5 and Examples 1-4, if the VA content in the polyolefin resin is too high or too low, the water breakdown resistance of the polyolefin composition prepared therefrom is decreased and cannot meet the requirements. This can be due to the fact that when the VA content is too low, the non-polar end of the attracted amphiphilic surfactant is less, resulting in the polar end of the amphiphilic surfactant being on the outside, the hydrophilicity being increased, and water being easily entered into the inside of the polyolefin composition, thus resulting in the decrease of the water breakdown resistance. When the VA content is too high, the polarity of the surface of the polyolefin composition is strong, resulting in the increase of the hydrophilicity, thus resulting in the decrease of the water breakdown resistance.

[0095] As can be seen from Comparative Example 6, if no coupling agent is added, even if the amphiphilic surfactant is added and the VA content in the polyolefin resin is adjusted, the water breakdown resistance of the polyolefin composition prepared therefrom still cannot meet the requirements.

[0096] Obviously, the above examples of the present application are merely illustrative for clearly explaining the present application, 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 of ordinary skill in the art. Here, it is not necessary and also impossible to exhaust all the embodiments. Any modification, equivalent replacement and improvement, etc. made 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 low smoke zero halogen polyolefin composition for waterborne photovoltaics, characterized in that, The composition comprises the following components by weight: Polyolefin resin 15-90 parts; Polyolefin grafted maleic anhydride 3-10 parts; Halogen-free flame retardant 50-100 parts; Coupling agent 0.3-2 parts; Surfactant 0.3-1 part; Crosslinking aid 0.5-2 parts; The polyolefin resin has a vinyl acetate content of 14wt%-26wt%; the surfactant has a hydroxyl value of 25-60mgKOH / g; and the surfactant comprises one or more of ethoxylated amide wax, polyoxyethylene ether or polyethylene glycol.

2. The low smoke zero halogen polyolefin composition for waterborne photovoltaics of claim 1, wherein, The surfactant has a hydroxyl value of 30-50mgKOH / g.

3. The low smoke zero halogen polyolefin composition for waterborne photovoltaics of claim 1, wherein, The polyolefin resin comprises 0-25 parts of polyethylene, 15-40 parts of ethylene-vinyl acetate, and 0-25 parts of POE.

4. The low smoke zero halogen polyolefin composition for waterborne photovoltaics of claim 1, wherein, The coupling agent comprises a silane coupling agent and / or a titanate coupling agent.

5. The low smoke zero halogen polyolefin composition for waterborne photovoltaics of claim 1, wherein, The halogen-free flame retardant is a hydroxide flame retardant.

6. The low smoke zero halogen polyolefin composition for waterborne photovoltaics of claim 1, wherein, The crosslinking aid is one or more of triallyl isocyanurate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.

7. The low smoke zero halogen polyolefin composition for waterborne photovoltaics of claim 1, wherein, 0.1-5 parts of an auxiliary are further included.

8. A process for the preparation of the low smoke halogen-free polyolefin composition for waterborne photovoltaics according to any one of claims 1 to 7, characterized in that, The method comprises the following steps: The components are mixed uniformly in a proportion by a banbury mixer, extruded and granulated by an extruder, and cooled to obtain.

9. Use of the low-smoke halogen-free polyolefin composition for waterborne photovoltaic as claimed in any one of claims 1-7 in the preparation of a waterborne photovoltaic cable sheath material.

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