Polyethylene composite material for rainwater collection module as well as preparation method and application of polyethylene composite material

Abstract

The invention relates to a polyethylene composite material for a rainwater collection module and a preparation method and application thereof in the field of polyethylene. The polyethylene composite material for the rainwater collection module comprises the following components in percentage by weight: 35-79% of high-density polyethylene resin; 20-45% of short glass fiber; 0.2% to 10% of polyfunctional amino phenyl silsesquioxane; 0.2 to 10% of a coupling agent; the polyethylene composite material is good in compressive strength, has a good effect of reducing antioxidant migration, and is suitable for collection and utilization of rainwater in sponge cities.

Description

Technical Field

[0001] The present invention relates to the field of polyethylene, and more particularly to a polyethylene composite material for a rainwater collection module, and a preparation method and application thereof. Background Art

[0002] With the acceleration of urbanization and the shortage of water resources, the construction of sponge cities has gradually entered the public's field of vision. As one of the important products for sponge city construction, rainwater collection modules have the characteristics of convenient construction, high efficiency, and high water storage rate. They are widely used in the collection and reuse of urban rainwater. Due to different application conditions and geological environments, different requirements are put forward for the performance of rainwater collection modules. Among them, vertical compressive strength, lateral compressive strength, and oxidation induction time are the core indicators that determine whether the rainwater collection module can meet the 50-year use requirements.

[0003] At present, the rainwater module products on the market are mainly made of polyethylene and polypropylene materials. Compared with polypropylene material modules, polyethylene rainwater modules have the advantages of good toughness, strong impact resistance, and excellent low temperature resistance. However, there are also problems such as low modulus of polyethylene materials, which leads to low axial compressive strength and lateral compressive strength of the product. Secondly, since the rainwater collection module is immersed in the rainwater environment for a long time, various organic substances in the water can cause the antioxidants in the material to migrate into the water, resulting in a rapid decline in product performance and a reduction in service life.

[0004] Therefore, the development of an antioxidant migration, high modulus polyethylene composite material has important economic and social benefits for the collection and reuse of urban rainwater. Summary of the invention

[0005] In order to solve the above problems existing in the prior art, the present invention proposes a polyethylene composite material for rainwater collection module. Specifically, it relates to a polyethylene composite material for rainwater collection module and a preparation method and application thereof. The polyethylene composite material has high tensile modulus, good impact resistance, high tolerance to organic matter in rainwater, and antioxidant in the material is not easy to migrate.

[0006] One of the purposes of the present invention is to provide a polyethylene composite material for a rainwater collection module. Taking the total weight of the polyethylene composite material for a rainwater collection module as 100%, the polyethylene composite material may include the following components in weight percentage:

[0007]

[0008] In specific practice, the polyethylene composite material for rainwater collection module may further include carbon black masterbatch. Taking the total weight of the polyethylene composite material for rainwater collection module as 100%, the following components may be included in weight percentage:

[0009]

[0010] In specific practice, the polyethylene composite material for rainwater collection module may further include an antioxidant. Taking the total weight of the polyethylene composite material for rainwater collection module as 100%, the following components may be included in weight percentage:

[0011]

[0012] in,

[0013] The amount of high-density polyethylene resin can be 35%, 37%, 40%, 42%, 45%, 47%, 50%, 55%, 60%, 65%, 70%, 75%, 79% or any value between the above values ​​or a numerical range between any two of the above values;

[0014] The amount of short glass fibers may be 20%, 22%, 25%, 27%, 30%, 32%, 35%, 37%, 40%, 42%, 45%, or any value between the above values ​​or a numerical range between any two of the above values;

[0015] The polyfunctional aminophenylsilsesquioxane may be 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or any value between the above values ​​or a numerical range between any two of the above values;

[0016] The amount of the coupling agent may be 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or any value between the above values ​​or a numerical range between any two of the above values;

[0017] The amount of carbon black masterbatch can be 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 2%, 3%, 4%, 5% or any value between the above values ​​or a numerical range between any two of the above values;

[0018] The amount of antioxidant used can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 2%, 3%, 4%, 5%, 6% or any value between the above values ​​or a numerical range between any two of the above values.

[0019] The high-density polyethylene resin may have a melt mass flow rate (190°C, 5kg) of 0.1-1.0g / 10min, preferably 0.10-0.60g / 10min, more preferably 0.20-0.30g / 10min; for example, it may be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0g / 10min or any value between the above values ​​or a numerical range between any two of the above values.

[0020] and / or,

[0021] The high-density polyethylene resin may have a density of 0.850-0.990 g / cm 3 , preferably 0.930-0.980 g / cm 3 , more preferably 0.94-0.96 g / cm 3 .

[0022] The DBP absorption value of the carbon black masterbatch may be 40-400 ml / 100 g, preferably 300-350 ml / 100 g, and / or the particle size of the carbon black masterbatch may be 5-100 nm, preferably 10-60 nm, more preferably 10-30 nm. For example, it may be 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70, 75, 80, 85, 90, 95, 100 nm, or any value between the above values, or a numerical range between any two of the above values.

[0023] The length of the short glass fibers may be 0.2-6 mm, preferably 0.5-4 mm; and / or, for example, may be 0.2, 0.5, 0.8, 1.0, 1.2, 1.5, 2.0, 2.2, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0 mm or any value therebetween or a numerical range between any two of the above values.

[0024] The monofilament diameter of the short glass fibers may be 6-13 μm, preferably 9-11 μm, for example, 6, 7, 8, 9, 10, 11, 12, 13 μm, or any value therebetween or a numerical range between any two of the above values.

[0025] The multifunctional aminophenylsilsesquioxane (APS) can be selected from one or more of diaminophenylsilsesquioxane, triaminophenylsilsesquioxane, and tetraaminophenylsilsesquioxane. For example, the structural formula of tetraaminophenylsilsesquioxane can be as follows (I).

[0026]

[0027] The coupling agent can be selected from silane coupling agents. Typical silane coupling agents can be one or more of A151 (vinyl triethoxysilane), A171 (vinyl trimethoxysilane), A172 (vinyl tri(β-methoxyethoxy) silane); A171 (vinyl trimethoxysilane) is more preferred.

[0028] The antioxidant can be an antioxidant commonly used in the field of polyethylene in the prior art, preferably a hindered phenol antioxidant. The hindered phenol antioxidant is more preferably at least one selected from tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate n-octadecyl ester, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid.

[0029] The composite material may include components including high-density polyethylene resin, optional antioxidant, optional carbon black masterbatch, short glass fiber, multifunctional aminophenylsilsesquioxane, and coupling agent. High-density polyethylene resin is used as the base resin, antioxidant and carbon black masterbatch can effectively improve the anti-aging performance of the material, short glass fiber can greatly improve the tensile strength of the composite material, and coupling agent can improve the compatibility of short glass fiber and polyethylene resin, so that the composite material is mixed more uniformly. Multifunctional aminophenylsilsesquioxane (APS) is a hybrid material, and the inorganic phase and the organic phase are bonded by covalent bonds. The performance of the material is between the corresponding inorganic and organic polymers. The cage-shaped core in the body structure will inhibit the movement of the polymer chain like the iron anchor of a ship, and even generate crystal domains in the polymer matrix, which can generate bonds between the polymer and the antioxidant to prevent the migration of the antioxidant.

[0030] The method for preparing the polyethylene composite material for rainwater collection module according to the second object of the present invention may include the following steps:

[0031] The short glass fibers pretreated with coupling agents, optional carbon black masterbatch and a mixture of multifunctional aminophenylsilsesquioxane (if the carbon black masterbatch is not contained, the multifunctional aminophenylsilsesquioxane is directly used), high-density polyethylene resin and optional antioxidant are melt-blended to obtain the product.

[0032] The method for preparing the short glass fiber pretreated with a coupling agent may include the following steps:

[0033] The coupling agent is evenly sprayed on the short glass fibers, and mixed evenly to obtain a mixture (specifically, the mixture can be placed in a high-speed mixer and mixed for 0.5-1 hour to obtain a uniform mixture).

[0034] The method for preparing the mixture of the carbon black masterbatch and the multifunctional aminophenylsilsesquioxane (APS) may include the following steps:

[0035] The multifunctional aminophenylsilsesquioxane (APS) and the carbon black masterbatch are ground and mixed to obtain a uniformly dispersed mixture of the multifunctional aminophenylsilsesquioxane (APS) and the carbon black masterbatch; preferably, the grinding is performed in a ball mill.

[0036] In the specific implementation,

[0037] The method for preparing the polyethylene composite material for rainwater collection module may include the following steps:

[0038] (1) Short glass fiber pretreatment: Spray the coupling agent evenly on the short glass fiber and mix for 0.5-1h to obtain a uniform mixture. The mixing device can be a commonly used device in the art, such as a high-speed mixer.

[0039] (2) Preparing a mixture of APS and carbon black masterbatch: Place APS and carbon black masterbatch in a ball mill and grind and stir for 0.5-1 h to obtain a uniformly dispersed mixture of APS and carbon black masterbatch.

[0040] (3) Mix the mixture obtained in step (1), the mixture obtained in step (2), the high-density polyethylene resin, and the optional antioxidant (specifically, the mixture can be mixed for 0.5 to 2 hours) to obtain a uniformly mixed premix. The mixing device can be a commonly used device in the art, such as a high-speed mixer.

[0041] (4) Melt-blending and extruding the premix obtained in step (3) to obtain the polyethylene composite material of the present invention. The blending device can be a commonly used device in the art, such as a twin-screw extruder. The screw speed can be 100-300 rpm, and the extrusion temperature can be between 130-250°C.

[0042] (5) After drying, the polyethylene composite material obtained in step (4) is put into an injection molding machine to produce a rainwater collection module. The processing temperature of the injection molding machine can be between 150-250° C., thereby obtaining a polyethylene composite material rainwater collection module.

[0043] The third object of the present invention is to provide a rainwater collection module made of the polyethylene composite material for the rainwater collection module described in the first object of the present invention or a rainwater collection module made of the polyethylene composite material obtained by the preparation method described in the second object of the present invention.

[0044] A fourth object of the present invention is to provide an application of the polyethylene composite material for rainwater collection module described in one of the objects of the present invention or the polyethylene composite material prepared according to the preparation method described in the second object of the present invention.

[0045] The polyethylene composite material of the present invention has a good effect of reducing the migration of antioxidants and greatly improves the compressive strength, and is suitable for the collection and utilization of rainwater in sponge cities. DETAILED DESCRIPTION

[0046] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0047] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0048] Source of raw materials

[0049] The raw materials used in the examples and comparative examples, unless otherwise specified, are disclosed in the prior art, for example, they can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0050] Embodiment 1:

[0051] Ingredients:

[0052] High-density polyethylene resin 57wt%; brand PN049, China Petrochemical Corporation, melt flow rate 0.27g / 10min (190℃, 5kg), density 0.947g / cm 3 ;

[0053] Antioxidant 0.5wt%; brand 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), Nanjing Milan Chemical Co., Ltd.;

[0054] Carbon black masterbatch 2wt%; brand HD2776, Cabot, DBP absorption value 330ml / 100g, particle size 24nm;

[0055] Short glass fiber 35wt%; brand CHOPVANTAGEHP3270, American PPG, glass fiber length 1.2mm, single fiber diameter 10μm;

[0056] APS 5wt%: 2wt% of diaminophenylsilsesquioxane and 3wt% of tetraaminophenylsilsesquioxane. The preparation method can refer to the following literature: Du Jianke, Yang Rongjie. Synthesis and Characterization of Cage-Shaped Octa(Aminophenyl)Silsesquioxane, Journal of Beijing Institute of Technology, 2007, Vol. 27, No. 4, 358-261.

[0057] Silane coupling agent 0.5wt%; brand: A171, Nanjing Quanxi Chemical Co., Ltd.

[0058] Preparation method:

[0059] (1) Pretreatment of short glass fibers: Spray the silane coupling agent evenly on the short glass fibers and mix them in a high-speed mixer for 0.8 h to obtain a uniform mixture.

[0060] (2) Preparation of a mixture of APS and carbon black masterbatch: Place the APS and carbon black masterbatch in a ball mill and grind and stir for 1 hour to obtain a uniformly dispersed mixture of APS and carbon black.

[0061] (3) Add the mixture obtained in step (1), the mixture obtained in step (2), an antioxidant, and a high-density polyethylene resin into a high-speed mixer and mix for 0.8 hours to obtain a uniformly mixed premix.

[0062] (4) feeding the premix obtained in step (3) into a twin-screw extruder for melt blending and extrusion granulation, with the screw speed being 200 rpm and the extrusion temperature being between 170° C. and 250° C., to obtain the polyethylene composite material of the present invention;

[0063] (5) After drying, the polyethylene composite material obtained in step (4) is put into an injection molding machine to produce a rainwater collection module. The processing temperature of the injection molding machine is between 170-250° C. to obtain a polyethylene composite material rainwater collection module.

[0064] Embodiment 2:

[0065] Ingredients:

[0066] High-density polyethylene resin 52wt%; brand YGH041T, Shanghai Petrochemical, melt flow rate 0.25g / 10min (190℃, 5kg), density 0.950g / cm 3 ;

[0067] Antioxidant 0.5wt%; brand 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), Nanjing Milan Chemical Co., Ltd.;

[0068] Carbon black masterbatch 1.7wt%; brand UN2014, Cabot, DBP absorption value 340ml / 100g, particle size 25nm;

[0069] Short glass fiber 40wt%; 568H, Jushi Co., Ltd., glass fiber length 1.5mm, single fiber diameter 10μm;

[0070] APS 5wt%: 2wt% triaminophenylsilsesquioxane, 3wt% tetraaminophenylsilsesquioxane. The preparation method can refer to the following literature: Du Jianke, Yang Rongjie. Synthesis and Characterization of Cage-Shaped Octa(Aminophenyl)Silsesquioxane, Journal of Beijing Institute of Technology, 2007, Vol. 27, No. 4, 358-261.

[0071] Silane coupling agent 0.8wt%; brand: A171, Nanjing Quanxi Chemical Co., Ltd.

[0072] Preparation method:

[0073] (1) Pretreatment of short glass fibers: Spray the silane coupling agent evenly on the short glass fibers and mix them in a high-speed mixer for 1 hour to obtain a uniform mixture.

[0074] (2) Preparation of a mixture of APS and carbon black masterbatch: Place the APS and carbon black masterbatch in a ball mill and grind and stir for 1 hour to obtain a uniformly dispersed mixture of APS and carbon black.

[0075] (3) Add the mixture obtained in step (1), the mixture obtained in step (2), an antioxidant, and a high-density polyethylene resin into a high-speed mixer and mix for 1 hour to obtain a uniformly mixed premix.

[0076] (4) feeding the premix obtained in step (3) into a twin-screw extruder for melt blending and extrusion granulation, with the screw speed being 200 rpm and the extrusion temperature being between 170° C. and 250° C., to obtain the polyethylene composite material of the present invention;

[0077] (5) After drying, the polyethylene composite material obtained in step (4) is put into an injection molding machine to produce a rainwater collection module. The processing temperature of the injection molding machine is between 170-250° C. to obtain a polyethylene composite material rainwater collection module.

[0078] Comparative Example 1:

[0079] Ingredients:

[0080] High-density polyethylene resin: 97wt%, brand HE3490LSH, Borealis, melt flow rate 0.25g / 10min (190℃, 5kg), density 0.951g / cm 3 ;

[0081] Carbon black masterbatch 2.5wt%; brand HD2776, Cabot;

[0082] Antioxidant 0.5wt%; brand 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), Nanjing Milan Chemical Co., Ltd.

[0083] Preparation method:

[0084] (1) Add carbon black masterbatch, antioxidant and high-density polyethylene resin into a high-speed mixer and mix for 1 hour to obtain a uniformly mixed premix.

[0085] (2) feeding the premix obtained in step (1) into a twin-screw extruder for melt blending and extrusion granulation, with the screw speed being 200 rpm and the extrusion temperature being between 170° C. and 250° C., to obtain a polyethylene composite material;

[0086] (3) After drying, the polyethylene composite material obtained in step (2) is put into an injection molding machine to produce a rainwater collection module. The processing temperature of the injection molding machine is between 170-250° C. to obtain a polyethylene composite material rainwater collection module.

[0087] Comparative Example 2:

[0088] Ingredients:

[0089] High-density polyethylene resin: 97wt%, brand YGH041T, Shanghai Petrochemical;

[0090] Carbon black masterbatch 2.5wt%; brand UN2014, Cabot;

[0091] Antioxidant 0.5wt%; brand 1010 (pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), Nanjing Milan Chemical Co., Ltd.

[0092] Preparation method:

[0093] (1) Add carbon black masterbatch, antioxidant and high-density polyethylene resin into a high-speed mixer and mix for 1 hour to obtain a uniformly mixed premix.

[0094] (2) feeding the premix obtained in step (1) into a twin-screw extruder for melt blending and extrusion granulation, with the screw speed being 200 rpm and the extrusion temperature being between 170° C. and 250° C., to obtain a polyethylene composite material;

[0095] (3) After drying, the polyethylene composite material obtained in step (2) is put into an injection molding machine to produce a rainwater collection module. The processing temperature of the injection molding machine is between 170-250° C. to obtain a polyethylene composite material rainwater collection module.

[0096] The samples prepared in the embodiment and the comparative example were divided into 4 groups respectively. One group was soaked in tap water and then subjected to an oxidation induction time performance test. The other three groups were subjected to an axial compressive strength test. The specific results are shown in Tables 1 and 2.

[0097] The immersion test conditions are: cut a 10 cm sample and immerse it in fresh tap water at a temperature of 80°C.

[0098] The oxidation induction time test was carried out at 200°C according to standard GB / T 19466.6-2009.

[0099] Axial compressive strength tests were performed at 23°C according to EN 17150:2009 Method A.

[0100] Table 1 Oxidation induction time after immersion

[0101]

[0102] Table 2 Axial compressive strength

[0103]

[0104] It can be seen from the data in Table 1 that in Example 1 and Example 2, due to the addition of short glass fibers, when the immersion time is 0 h, the initial oxidation induction time of Example 1 and Example 2 is lower than that of Comparative Example 1 and Comparative Example 2, but after the immersion time is 1000 h, the oxidation induction time of Example 1 and Example 2 is much greater than that of Comparative Example 1 and Comparative Example 2.

[0105] It can be seen from the data in Table 1 and Table 2 that the rainwater collection module produced by the invention has excellent performance, greatly improved compressive strength, and has a good effect of reducing antioxidant migration, and is more suitable for the collection and utilization of rainwater in sponge cities.

Claims

1. A polyethylene composite material for rainwater collection module, characterized in that Taking the total weight of the polyethylene composite material for rainwater collection module as 100%, the following components are included in weight percentage:

2. The polyethylene composite material for rainwater collection module according to claim 1, characterized in that Taking the total weight of the polyethylene composite material for rainwater collection module as 100%, the following components are included in weight percentage:

3. The polyethylene composite material for rainwater collection module according to claim 1 or 2, characterized in that: The high-density polyethylene resin has a melt mass flow rate (190° C., 5 kg) of 0.1-1.0 g / 10 min, preferably 0.10-0.60 g / 10 min; and / or, The high-density polyethylene resin has a density of 0.850-0.990 g / cm 3 , preferably 0.930-0.980 g / cm 3 , more preferably 0.940-0.960 g / cm 3 .

4. The polyethylene composite material for rainwater collection module according to claim 1 or 2, characterized in that: The length of the short glass fibers is 0.2-6 mm, preferably 0.5-4 mm; and / or, The monofilament diameter of the short glass fibers is 6-13 μm, preferably 9-11 μm.

5. The polyethylene composite material for rainwater collection module according to claim 1 or 2, characterized in that: The multifunctional aminophenylsilsesquioxane (APS) is selected from one or more of diaminophenylsilsesquioxane, triaminophenylsilsesquioxane, and tetraaminophenylsilsesquioxane.

6. The polyethylene composite material for rainwater collection module according to claim 1 or 2, characterized in that: The coupling agent is selected from silane coupling agents, preferably one or more of A151 (vinyl triethoxysilane), A171 (vinyl trimethoxysilane), A172 (vinyl tri(β-methoxyethoxy) silane); more preferably A171 (vinyl trimethoxysilane).

7. The polyethylene composite material for rainwater collection module according to claim 2, characterized in that: The DBP absorption value of the carbon black masterbatch is 40-400 ml / 100 g; preferably 300-350 ml / 100 g; and / or, The particle size of the carbon black masterbatch is 5-100 nm, preferably 10-60 nm, preferably 10-30 nm.

8. The method for preparing the polyethylene composite material for rainwater collection module according to any one of claims 1 to 7, characterized in that The following steps are involved: The components including short glass fibers pretreated with coupling agents, optional carbon black masterbatch, a mixture of multifunctional aminophenylsilsesquioxane and high-density polyethylene resin are melt-blended to obtain the product.

9. The method for preparing the polyethylene composite material for rainwater collection module according to claim 8, characterized in that: The method for preparing short glass fibers pretreated with a coupling agent comprises the following steps: The coupling agent is sprayed on the short glass fibers and mixed evenly to obtain a mixture.

10. The method for preparing the polyethylene composite material for rainwater collection module according to claim 8, characterized in that: The method for preparing the mixture of carbon black masterbatch and multifunctional aminophenylsilsesquioxane comprises the following steps: The multifunctional aminophenyl silsesquioxane and the carbon black masterbatch are ground and mixed to obtain a uniformly dispersed mixture of the multifunctional aminophenyl silsesquioxane and the carbon black masterbatch; preferably, the grinding is performed in a ball mill.

11. A rainwater collection module made of the polyethylene composite material for rainwater collection module according to any one of claims 1 to 7 or the polyethylene composite material obtained by the preparation method according to any one of claims 8 to 10.

12. Use of the polyethylene composite material for rainwater collection module according to any one of claims 1 to 7 or the polyethylene composite material prepared according to the preparation method according to any one of claims 8 to 10.

Images