Polyolefin composite material, method for producing the same, and use thereof

Abstract

This invention discloses a polyolefin composite material, its preparation method, and its application. The polyolefin composite material comprises the following components by weight: 38-68 parts polyolefin resin; 78-158 parts halogen-free flame retardant; 1-2 parts crosslinking aid; 5-16 parts polysilsesquioxane; and 3-16 parts magnesite. By using polyolefin resin as the matrix resin and adding a halogen-free flame retardant, in conjunction with polysilsesquioxane and magnesite, this invention enables the prepared polyolefin composite material to meet B1 flame retardancy requirements while also exhibiting the property of not producing dripping material within 1200 seconds. It is particularly suitable for use as insulation material for electrical wiring in airports, shopping malls, subways, and other similar locations.

Description

Technical Field

[0001] This invention belongs to the field of cable material technology, specifically relating to a polyolefin composite material, its preparation method, and its application. Background Technology

[0002] my country's engineering building fire protection codes have increasingly stringent requirements for fire protection in densely populated places, high-rise buildings and special places. The Civil Building Electrical Fire Protection Design Code clearly stipulates that cables laid in the vertical shafts of high-rise buildings higher than 100 meters and less than 250 meters, wires laid in refuge floors and refuge rooms, underground buildings where people stay for a long time, and cables laid in the ceiling and passing through fire protection zones should be B1 / B2 grade high flame-retardant cables.

[0003] Existing B1-grade flame-retardant cables tend to produce excessive dripping, making it difficult to meet the d0 rating for burning droplets / particulates as specified in GB 31247-2014. This could potentially lead to the spread of a fire or secondary fire. Building design typically requires materials to meet the d0 rating. Therefore, there is a need in this field to develop a polyolefin composite material with good flame-retardant properties that also prevents burning droplets. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects or deficiencies in the above-mentioned polyolefin composite materials and to provide a polyolefin composite material.

[0005] Another object of the present invention is to provide a method for preparing the above-mentioned polyolefin composite material.

[0006] Another object of the present invention is to provide applications of the above-described polyolefin composite material.

[0007] To achieve the above objectives, the present invention employs the following technical solution:

[0008] A polyolefin composite material comprising the following components in parts by weight:

[0009]

[0010] In this invention, by selecting polyolefin resin as the matrix resin and adding a halogen-free flame retardant, synergistically combining magnesite and polysilsesquioxane, the polyolefin composite material can meet B1 combustion requirements while preventing dripping within 1200 seconds. Specifically, the addition of polysilsesquioxane can significantly increase flame retardant performance, reduce the size of the combustion flame, and prevent it from spreading. However, its high decomposition temperature is not conducive to char formation in the early stages of combustion, which may lead to slight dripping. Adding a certain amount of magnesite facilitates the formation of a dense inorganic salt structure with polysilsesquioxane, providing significant protection in the early stages of combustion and ensuring the strength of the carbon layer during combustion, preventing dripping.

[0011] It should be noted that, in the polyolefin composite material described in this invention, the content of polyolefin resin is preferably not less than 15 wt%.

[0012] Furthermore, in the polyolefin composite material, the content of polyolefin resin is preferably not less than 50 wt% of the matrix resin.

[0013] In this invention, the polysilsesquioxane is 5 to 16 parts, for example, but not limited to, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts, 15 parts, 15.5 parts, or 16 parts, or any range between the above values.

[0014] In this invention, the hydromagnesite is 3 to 6 parts, for example, but not limited to 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 10.5 parts, 11 parts, 11.5 parts, 12 parts, 12.5 parts, 13 parts, 13.5 parts, 14 parts, 14.5 parts, 15 parts, 15.5 parts, or 16 parts, or any range between the above values.

[0015] Furthermore, the polysilsesquioxane is (RSiO) 3 / 2 ) n n is an integer between 1 and 16.

[0016] Specifically, n can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16.

[0017] Furthermore, n is 6 to 14; even further, n is 8 to 12.

[0018] Furthermore, the silicon content in the polysilsesquioxane is 15-50 wt%.

[0019] Further, R is an alkyl group having 4 to 12 carbon atoms, an epoxy group having 4 to 12 carbon atoms, an amino group having 4 to 12 carbon atoms, a phenyl group, or a siloxane group having 2 to 12 carbon atoms.

[0020] Furthermore, R is a siloxane and / or phenyl group having 2 to 12 carbon atoms.

[0021] Furthermore, the polysilsesquioxane is a cage-like polysilsesquioxane.

[0022] Furthermore, the grain size D50 of the hydromagnesite is ≤8μm, for example, but not limited to ≤8μm, 7.5μm, 7μm, 6.5μm, 6μm, 5.5μm, 5μm, 4.5μm, 4μm, 3.5μm, 3μm, 2.5μm, 2μm, 1.5μm or 1μm, etc.

[0023] Furthermore, the particle size D90 of the hydromagnesite is 2–5 μm.

[0024] Furthermore, the mass ratio of the polysilsesquioxane to hydromagnesite is (0.3-5):1.

[0025] Furthermore, the mass ratio of the polysilsesquioxane to hydromagnesite is (1.5–4.5):1.

[0026] Furthermore, the halogen-free flame retardant is a hydroxide flame retardant.

[0027] Furthermore, the hydroxide flame retardant includes magnesium hydroxide and / or aluminum hydroxide.

[0028] Furthermore, the average particle size of the hydroxide flame retardant is 0.6–3.0 μm.

[0029] Furthermore, the polyolefin resin includes one or more of polyethylene resin, ethylene-vinyl acetate, ethylene methacrylate, ethylene butyl acrylate, or POE.

[0030] In some preferred embodiments, the polyolefin resin is polyethylene resin, ethylene-vinyl acetate and POE in a mass ratio of 1:(2-4):(2-4).

[0031] In some specific embodiments, the polyolefin resin is ethylene-vinyl acetate and POE in a mass ratio of 1:(0.5-2).

[0032] Specifically, the melt flow rate of the polyethylene resin at 190°C and a load of 2.16 kg is 0.2–5 g / 10 min.

[0033] Specifically, the test standard for the melt flow rate of the polyethylene resin is GB / T 3682-2000.

[0034] Specifically, the melt flow rate of the ethylene-vinyl acetate at 190°C and a load of 2.16 kg is 2–10 g / 10 min.

[0035] Specifically, the test standard for the melt flow rate of the ethylene-vinyl acetate is GB / T 3682-2000.

[0036] Specifically, the vinyl acetate content in the ethylene-vinyl acetate ester is 14-30 wt%.

[0037] Specifically, the POE is an ethylene-octene copolymer.

[0038] Specifically, the POE has a melt flow rate of 0.1 to 6 g / 10 min at 190°C and a load of 2.16 kg.

[0039] Specifically, the test standard for the melt flow rate of the POE is GB / T 3682-2000.

[0040] Furthermore, the crosslinking aid is one or more of triallyl isocyanurate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.

[0041] Furthermore, the polyolefin composite material also includes 0.1 to 5 parts of additives.

[0042] Specifically, the additives include, but are not limited to, one or more of antioxidants, lubricants, weathering agents, or colorants.

[0043] In this invention, commonly used antioxidants can be selected, such as, but not limited to, one or more of hindered phenolic antioxidants, phosphite antioxidants, or thioester antioxidants.

[0044] Specifically, the hindered phenolic antioxidants are N,N'-hexamethylene bis(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), and octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl)propionate (Irganox 1098). 1076) or one or more of 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acrylic acid]-1,1-dimethyl}-2,4,8,10-tetraoxaspirocycloundecane (ADK AO-80).

[0045] The phosphite antioxidant is one or more of tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168), bis(2,6-di-tert-butyl-4-tolyl) pentaerythritol phosphite (PEP-36), or 627A.

[0046] The thioester antioxidant is one or more of the following: distearate thiodipropionate, dodecyl thiodipropionate (antioxidant DLTDP), dilaurate thiodipropionate, or pentaerythritol-based dodecyl thiopropionate.

[0047] The present invention may use commonly used lubricants, such as, but not limited to, one or more of vinyl bis-stearamide, polysiloxane, calcium stearate, magnesium stearate, zinc stearate, silicone, PE wax, or PP wax.

[0048] In this invention, commonly used weathering agents can be selected according to existing technology, such as, but not limited to, hindered amine light stabilizers and benzotriazole ultraviolet absorbers.

[0049] Specifically, the hindered amine light stabilizer is 2,2,6,6-tetramethyl-4-piperidine stearate and / or bis(2,2,6,6-tetramethyl-4-piperidine) sebacate.

[0050] Furthermore, the polyolefin composite material comprises the following components calculated in parts by weight:

[0051]

[0052] This invention also protects a method for preparing the above-mentioned polyolefin composite material, comprising the following steps:

[0053] After mixing the components, the polyolefin composite material is obtained by intensive mixing and extrusion granulation.

[0054] Furthermore, the mixing temperature is 140–160°C.

[0055] Furthermore, the mixing speed is 40-50 rpm.

[0056] Furthermore, the extrusion temperature is 120–150°C.

[0057] Furthermore, the extrusion speed is 200–400 rpm.

[0058] This invention also protects the use of the above-mentioned polyolefin composite material in the manufacture of household goods, electronic components, household appliances, gardening equipment, medical technology equipment, motor vehicle parts, and vehicle body parts. In particular, the application of the above-mentioned polyolefin composite material in the manufacture of cable materials is especially suitable for use as insulation material for electrical wires in airports, shopping malls, subways, and other similar locations.

[0059] Compared with the prior art, the present invention has the following beneficial effects:

[0060] This invention provides a polyolefin composite material. By using polyolefin resin as the matrix resin and adding a halogen-free flame retardant, along with polysilsesquioxane and hydromagnesia, the resulting polyolefin composite material can meet the B1 flame retardancy rating while also exhibiting the property of not producing dripping material within 1200 seconds. Detailed Implementation

[0061] The present invention will be further described in detail below with reference to specific embodiments. These embodiments are only used to explain the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods; the materials and reagents used are commercially available unless otherwise specified.

[0062] 1. Raw materials used in each embodiment and comparative example:

[0063] Polyolefin resin:

[0064] Polyethylene (PE): LLDPE 3812PA, purchased from ExxonMobil;

[0065] Ethylene-vinyl acetate copolymer (EVA): EVA 7470M, purchased from Taiwan Plastics Industries Co., Ltd., Taiwan Province, China;

[0066] POE: POE 58750, purchased from Dow Chemical;

[0067] Halogen-free flame retardant:

[0068] Halogen-free flame retardant 1: Aluminum hydroxide, OL-104LEO, purchased from Martin, Germany;

[0069] Halogen-free flame retardant 2: Magnesium hydroxide, H-5, purchased from Albemarle, USA;

[0070] Polysilsesquioxane:

[0071] Polysilsesquioxane 1:dodecyl POSS, (RSiO 3 / 2 ) 12 R stands for phenyl, purchased from Hybrid Plastics;

[0072] Polysilsesquioxane 2: Octaisobutylated POSS, (RSiO 3 / 2 )8,R is isobutyl, purchased from Hybrid Plastics;

[0073] Polysilsesquioxane 3:octamethylsiloxane-based POSS, (RSiO 3 / 2 )8,R is HMe2SiO-, purchased from HybridPlastics;

[0074] Hydromagnesite:

[0075] Hydromagnesite 1: Grain size D50 is 2.5μm, purchased from Jiangsu Xibeli;

[0076] Hydromagnesite 2: Particle size D50 is 4.0μm, purchased from Guangyuan Chemical;

[0077] Crosslinking aid: Triallyl isocyanurate, commercially available;

[0078] Antioxidants: The compound of antioxidant 1790, antioxidant 168 and antioxidant DLTDP in a mass ratio of 3:1:2 is commercially available; it should be noted that the same raw materials were used in the parallel experiments of the embodiments and comparative examples of this invention.

[0079] 2. The polyolefin composite materials described in each embodiment and comparative example were prepared according to the formulations in Tables 1-2 by the following method:

[0080] After mixing the components in proportion, the mixture is transferred to an internal mixer at a speed of 40-50 rpm and a temperature of 140-160°C. After mixing, the mixture is fed into an extruder for granulation at a temperature of 120-150°C and a speed of 200-400 rpm. After pelletizing and cooling, the polyolefin composite material is obtained.

[0081] 3. Performance Testing

[0082] (1) The polyolefin composite materials prepared in each embodiment and comparative example were extruded to a thickness of 2.5 mm. 2 After the cable is irradiated and cross-linked, its combustion performance and dripping condition are tested according to standard GB / T 31248-2014.

[0083] Ratings are conducted according to GB / T 31247-2014; among them, the B1 flame retardant rating requires flame spread ≤1.5m, peak heat release rate ≤30kW, total heat release ≤15MJ, combustion growth rate index ≤150W / s, and peak smoke production rate ≤0.25m. 2 / s, total smoke production ≤50m 2 d0: No burning droplets / particles within 1200s; d1: Burning droplets / particles lasting no more than 10s within 1200s; d2: Not reaching d1 level.

[0084] Examples 1-8 and Comparative Examples 1-6

[0085] Table 1. Amounts (parts by weight) and properties of each component in the polyolefin composites of Examples 1-8

[0086]

[0087] Table 2 shows the dosage (parts by weight) and properties of each component in the polyolefin composites of Comparative Examples 1–6.

[0088] Comparative Example 1 2 3 4 5 6 PE 10 10 10 10 10 10 EVA 25 25 25 25 25 25 POE 25 25 25 25 25 25 Halogen-free flame retardant 1 75 75 75 75 75 75 Halogen-free flame retardant 2 75 75 75 75 75 75 Crosslinking aids 1.5 1.5 1.5 1.5 1.5 1.5 Polysilsesquioxane 1 / 10 2.5 10 16 / Hydromagnesite 1 6 / 6 1.5 / 16 antioxidants 1 1 1 1 1 1 Carbonization height FS(m) 1.8 1.5 1.3 1.4 1.2 1.7 Peak heat release HRR (kW) 36 30 31 29 26 33 Total heat release (THR) (MJ) 17 15 16 14 13 16 FIGRA (W / s) index for combustion growth rate 112 114 102 104 98 108 <![CDATA[Peak smoke production rate SPR (m 2 / s)]]> 0.13 0.14 0.11 0.12 0.15 0.13 <![CDATA[Total smoke production TSP (m 2 )]]> 42 45 35 37 47 43 B1 flame retardant rating Unqualified qualified Unqualified qualified qualified Unqualified dripping situation d2 d1 d2 d1 d1 d2

[0089] As can be seen from Table 1, the polyolefin composite material prepared by the present invention has good flame retardant properties, which can meet the B1 flame retardant standard and have no burning drips within 1200s, which meets the d0 level in GB / T 31247-2014 standard.

[0090] As can be seen from Comparative Examples 1, 3, and 6, if magnesite or polysilsesquioxane is added alone in too low a quantity, the resulting polyolefin composite material cannot pass the B1 flame retardancy rating and has poor drip properties.

[0091] Comparative Examples 2, 4, and 5 show that if the amount of polysilsesquioxane or hydromagnesia added alone is too low, the resulting polyolefin composite material can meet the B1 flame retardancy rating, but it is prone to dripping during combustion and cannot reach the d0 rating.

[0092] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A polyolefin composite material, characterized in that, Includes the following components, calculated in parts by weight: 38-68 parts of polyolefin resin; 78-158 parts of halogen-free flame retardant; 1-2 parts of crosslinking aid; 5-16 parts of polysilsesquioxane; 3 to 16 parts of hydromagnesia.

2. The polyolefin composite material according to claim 1, characterized in that, said polysilsesquioxane is (RSiO 3 / 2 ) n , n is an integer between 1 and 16.

3. The polyolefin composite material according to claim 2, characterized in that, R is an alkyl group with 4 to 12 carbon atoms, an epoxy group with 4 to 12 carbon atoms, an amino group with 4 to 12 carbon atoms, a phenyl group, or a siloxane group with 2 to 12 carbon atoms.

4. The polyolefin composite material according to claim 1, characterized in that, The magnesite grain size D50 is ≤8μm.

5. The polyolefin composite material according to claim 1, characterized in that, The halogen-free flame retardant is a hydroxide flame retardant.

6. The polyolefin composite material according to claim 1, characterized in that, The polyolefin resin includes one or more of polyethylene resin, ethylene-vinyl acetate, ethylene methacrylate, ethylene butyl acrylate, or POE.

7. The polyolefin composite material according to claim 1, characterized in that, It also includes 0.1 to 5 parts of additives; the additives include one or more of antioxidants, lubricants, weathering agents or colorants.

8. A method for preparing the polyolefin composite material according to any one of claims 1 to 7, characterized in that, Includes the following steps: After mixing the components, the polyolefin composite material is obtained by intensive mixing and extrusion granulation.

9. The use of the polyolefin composite material according to any one of claims 1 to 7 in the preparation of cable materials.

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