Flame-retardant polydicyclopentadiene composite material with cross-linked interpenetrating network and preparation method of flame-retardant polydicyclopentadiene composite material

Abstract

The invention belongs to the technical field of modification of flame-retardant high polymer materials, and particularly relates to a flame-retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network and a preparation method of the flame-retardant polydicyclopentadiene composite material. The preparation method comprises the following steps: carrying out organic silicon modification on an acrylate compound, and preparing a reaction solution A from the organic silicon modified acrylate compound, a catalyst and a solvent; preparing a reaction solution B from thickened dicyclopentadiene and aluminum alkyl serving as an activating agent; reacting the reaction liquid A and the reaction liquid B, molding, curing and demolding to obtain a finished product. According to the invention, the organosilicone modified acrylate compound and dicyclopentadiene are injected into a mold, a parallel polymerization reaction is carried out by using a bi-component monomer to form a cross-linked interpenetrating network structure, and compared with the traditional additive flame-retardant polydicyclopentadiene, the material prepared by the invention has excellent molding processability and higher mechanical strength, and can be widely applied to the field of flame-retardant materials. A ceramic thermal insulation layer is rapidly formed in the combustion process, and the flame-retardant effect is excellent

Description

Technical Field

[0001] The invention belongs to the technical field of flame retardant polymer material modification, and particularly relates to a flame retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network and a preparation method thereof. Background Art

[0002] Polydicyclopentadiene (PDCPD) is an environmentally friendly material obtained by ring-opening polymerization of dicyclopentadiene (DCPD). The main chain has a variety of stable ring structures and carbon-carbon double bonds and a three-dimensional cross-linked network structure, which gives it good mechanical strength, weather resistance, coatability, acid and alkali resistance, etc. It is widely used in the fields of automobiles, home appliances, shipbuilding, medical equipment, industrial facilities, and aerospace equipment. However, PDCPD is composed of all hydrocarbons and is very easy to burn when exposed to fire. A large amount of smoke and toxic gases will be quickly formed during the combustion process, which limits the use of PDCPD.

[0003] In order to improve the flame retardancy of PDCPD, additive or reactive flame retardants are usually added to improve the flame retardant properties of the polymer. However, due to the inherent cross-linking structure of PDCPD and the limitations of the processing technology, the types of flame retardants that can be used for flame retardant modification of PDCPD are limited, and there are problems such as low flame retardant efficiency, large addition amount, and great impact on material processing and mechanical properties.

[0004] The intrinsic flame retardancy based on cross-linked interpenetrating network (IPN) is to embed the flame retardant unit into the polymer molecular chain in the form of covalent bonds, so that the flame retardant and the matrix material are connected in the form of covalent bonds, avoiding the adverse effects of large amount of flame retardant addition, flame retardant migration and oxidation on polymer processing and use. At the same time, the interpenetrating network allows the matrix and the flame retardant to cross-penetrate each other and mechanically entangle, playing the role of "forced mutual compatibility" and "synergistic effect", which is an effective way to achieve the preparation of high-performance flame retardants. The patent with application number CN201010598752.4 discloses a polydicyclopentadiene / polystyrene interpenetrating polymer network and its preparation method. By reacting and copolymerizing halogen-containing styrene with dicyclopentadiene, a flame retardant material with an interpenetrating network is obtained. However, the introduction of halogen elements in the polymerization process will release toxic and harmful gases, posing a threat to human health and the environment. Summary of the invention

[0005] The object of the present invention is to provide a flame retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network and a preparation method thereof, so as to solve the problems in the background technology.

[0006] The purpose of the present invention can be achieved by the following technical solutions: A method for preparing a polydicyclopentadiene composite material comprises the following steps: Preparation of organosilicon-modified acrylate compound: siloxane, acrylate compound and p-hydroxyanisole are added to a flask in sequence, nitrogen is introduced, the temperature is increased, pentaerythritol triacrylate is added dropwise, the temperature is increased, and the reaction is continued to obtain an organosilicon-modified acrylate compound; Dicyclopentadiene thickening treatment: Dicyclopentadiene and butadiene rubber are heated and stirred to obtain thickened dicyclopentadiene; Preparation of reaction solution A: under the protection of high-purity nitrogen, add the organosilicon-modified acrylate compound, the catalyst and the solvent into container A, and after the addition is completed, stir to obtain reaction solution A; Preparation of reaction solution B: under the protection of high-purity nitrogen, thickening dicyclopentadiene, initiator, and alkyl aluminum activator are added to container B. After the addition is completed, the reaction solution B is obtained after stirring; Molding: The reaction liquid A and the reaction liquid B are subjected to reaction injection molding to obtain a polydicyclopentadiene composite material.

[0007] It should be noted that the present invention modifies the acrylic acid ester compound with organosilicon, embeds the flame retardant unit into the acrylic acid ester molecular chain in the form of a covalent bond, and obtains a flame retardant composite material of dicyclopentadiene and acrylic acid ester having an interpenetrating network structure under reaction injection molding conditions. The organosilicon-modified acrylic acid ester has good mechanical strength and flame retardant properties, and has good synergistic benefits with polydicyclopentadiene, which makes up for the deficiencies of mechanical strength and flame retardant properties of polydicyclopentadiene; the acrylic acid ester and dicyclopentadiene react in parallel in the reaction injection molding mold to obtain a highly penetrating polymer network, which effectively improves the mechanical strength of the composite material; the siloxane in the composite material cross-links into carbon during the combustion process to form a dense ceramic carbon layer, which further improves the flame retardant properties of the composite material.

[0008] Furthermore, the step of preparing the organosilicon-modified acrylate compound also includes: adding siloxane, acrylate compound, and p-hydroxyanisole to a three-necked flask in sequence, introducing nitrogen, heating to 30-80° C., adding pentaerythritol triacrylate dropwise, heating to 50-100° C., and continuing the reaction for 0.5-3 hours to obtain the organosilicon-modified acrylate compound.

[0009] Furthermore, in the preparation of the organosilicon-modified acrylate compound, the siloxane includes one or more of vinyltrimethoxysilane, tetramethoxysilane, and trimethylmethoxysilane; the acrylate compound includes one or more of methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate; the mass ratio of the siloxane, the acrylate compound, and p-hydroxyanisole is 1-5:50-100:1; and the amount of pentaerythritol triacrylate added is 5-10g.

[0010] Furthermore, the step of thickening treatment of dicyclopentadiene also includes: heating dicyclopentadiene and butadiene rubber to 60-120° C. and stirring for 10-40 minutes to obtain thickened dicyclopentadiene.

[0011] Furthermore, in the dicyclopentadiene thickening treatment, the mass ratio of dicyclopentadiene to butadiene rubber is 5-10:1.

[0012] Furthermore, in the preparation of reaction solution A, the catalyst includes one or more of tungsten hexachloride, tungsten tetrabromide, and tungsten boride; the solvent includes one or more of methyl ethyl ketone, dichloromethane, and chloroform; and the mass ratio of the organosilicon-modified acrylate compound, the catalyst, and the solvent is 10-20:0.1-0.3:50-100.

[0013] Furthermore, in the preparation of reaction solution B, the initiator includes one or more of potassium persulfate, dibenzoyl peroxide, and azobisisoheptonitrile; the mass ratio of thickening dicyclopentadiene, initiator, and alkyl aluminum is 100-120:0.5-1:1-3.

[0014] Furthermore, the molding step also includes: rapidly injecting the reaction liquid A and the reaction liquid B into the mold through a single screw, the reaction injection molding temperature is 60-80°C, the holding pressure is 0.1-1 MPa, and the holding time is 5-30 min to obtain a polydicyclopentadiene composite material.

[0015] Furthermore, during the molding, the mass ratio of reaction liquid A to reaction liquid B is 3-7:7-3.

[0016] A flame-retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network is prepared according to the above-mentioned preparation method of a polydicyclopentadiene composite material.

[0017] Compared with the prior art, the present invention has the following beneficial effects: 1. Embed silicone into the polymer molecular chain in the form of covalent bonds to avoid the adverse effects of flame retardant addition on the mechanical properties of the composite material.

[0018] 2. Acrylate compounds have good mechanical strength and thermal stability, and have good synergistic effects with dicyclopentadiene, making up for the deficiencies in mechanical properties and heat resistance of dicyclopentadiene.

[0019] 3. The composite material with a highly interpenetrating network structure is formed by the reaction injection molding process, which is conducive to forming a uniform and dense ceramic carbon layer on the surface of the material and improving the flame retardant effect of the composite material. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings: Figure 1 It is a preparation flow chart of the composite material of the present invention. DETAILED DESCRIPTION

[0021] The technical solution of the present invention is described below through specific examples. It should be understood that the one or more method steps mentioned in the present invention do not exclude the existence of other method steps before and after the combination step or the insertion of other method steps between these explicitly mentioned steps; it should also be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. Moreover, unless otherwise specified, the numbering of each method step is only a convenient tool for identifying each method step, and is not intended to limit the order of arrangement of each method step or to limit the scope of the present invention. The change or adjustment of the relative relationship thereof shall also be regarded as the scope of the present invention without substantially changing the technical content.

[0022] In order to better understand the above technical scheme, the exemplary embodiments of the present invention are described in more detail below. Although exemplary embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present invention and to enable the scope of the present invention to be fully communicated to those skilled in the art.

[0023] In the following examples and comparative examples, unless otherwise specified, all raw materials are commercially available.

[0024] Among them, the manufacturer model of butadiene rubber is: Qilu Petrochemical, BR9000; the manufacturer model of alkyl aluminum is: Hubei Benuofu Chemical Technology Co., Ltd., tridodecyl aluminum.

[0025] The purity of all raw materials and reagents was selected to be 99%.

[0026] 1. Preparation of composite materials Example 1 Reference Figure 1 , a flame retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network and a preparation method thereof, the specific steps are as follows: Step 1: Weigh 10 g of vinyltrimethoxysilane, 500 g of methyl methacrylate and 10 g of p-hydroxyanisole, add into a 2000 mL three-necked flask, introduce nitrogen, heat to 60° C., add dropwise 5 g of pentaerythritol triacrylate, heat to 80° C., continue the reaction for 1 h, and obtain a silicone-modified acrylate compound.

[0027] Step 2: Weigh 500 g of dicyclopentadiene and 100 g of butadiene rubber, add them into a 2000 mL three-necked flask, heat to 95° C., and stir for 30 minutes to obtain thickened dicyclopentadiene.

[0028] Step 3: Under the protection of high-purity nitrogen, 100 g of organosilicon-modified acrylate compound, 1 g of tungsten hexachloride catalyst and 500 g of methyl ethyl ketone solvent are added into container A. After the addition is completed, reaction solution A is obtained after stirring.

[0029] Step 4: Under the protection of high-purity nitrogen, add 100 g thickening dicyclopentadiene, 0.5 g potassium persulfate initiator, and 1 g alkyl aluminum activator into container B. After the addition is completed, the reaction solution B is obtained after stirring.

[0030] Step 5: Weigh 30g of reaction liquid A and 70g of reaction liquid B, and quickly inject them into the mold through a single screw. The reaction injection molding temperature is 75°C, the holding pressure is 0.6 MPa, and the holding time is 10 minutes. Take out the sample for performance testing. The sample is a flame-retardant polydicyclopentadiene composite material.

[0031] Example 2 Reference Figure 1 , a flame retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network and a preparation method thereof, the specific steps are as follows: Step 1: Weigh 20 g of tetramethoxysilane, 600 g of ethyl methacrylate and 10 g of p-hydroxyanisole, add into a 2000 mL three-necked flask, introduce nitrogen, heat to 60° C., dropwise add 6 g of pentaerythritol triacrylate, heat to 80° C., continue the reaction for 1 h, and obtain a silicone-modified acrylate compound.

[0032] Step 2: Weigh 600 g of dicyclopentadiene and 100 g of butadiene rubber, add them into a 2000 mL three-necked flask, heat to 95° C., and stir for 30 minutes to obtain thickened dicyclopentadiene.

[0033] Step 3: Under the protection of high-purity nitrogen, 120 g of an organosilicon-modified acrylate compound, 1.5 g of a tungsten tetrabromide catalyst and 600 g of a dichloromethane solvent are added to a container A. After the addition is completed, a reaction solution A is obtained after stirring.

[0034] Step 4: Under the protection of high-purity nitrogen, 105 g of thickening dicyclopentadiene, 0.6 g of dibenzoyl peroxide initiator, and 1.5 g of alkyl aluminum activator are added to container B. After the addition is completed, reaction solution B is obtained after stirring.

[0035] Step 5: Weigh 40g of reaction liquid A and 60g of reaction liquid B, and quickly inject them into the mold through a single screw. The reaction injection molding temperature is 75°C, the holding pressure is 0.6 MPa, and the holding time is 10 minutes. Take out the sample for performance testing. The sample is a flame-retardant polydicyclopentadiene composite material.

[0036] Example 3 Reference Figure 1 , a flame retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network and a preparation method thereof, the specific steps are as follows: Step 1: Weigh 30 g of trimethylmethoxysilane, 700 g of n-butyl methacrylate and 10 g of p-hydroxyanisole, add into a 2000 mL three-necked flask, introduce nitrogen, heat to 60° C., dropwise add 7 g of pentaerythritol triacrylate, heat to 80° C., continue the reaction for 1 h, and obtain a silicone-modified acrylate compound.

[0037] Step 2: Weigh 700 g of dicyclopentadiene and 100 g of butadiene rubber, add them into a 2000 mL three-necked flask, heat to 95° C., and stir for 30 minutes to obtain thickened dicyclopentadiene.

[0038] Step 3: Under the protection of high-purity nitrogen, 140 g of an organosilicon-modified acrylate compound, 2.0 g of a tungsten boride catalyst and 700 g of a chloroform solvent are added to a container A. After the addition is completed, a reaction solution A is obtained after stirring.

[0039] Step 4: Under the protection of high-purity nitrogen, add 110 g of thickening dicyclopentadiene, 0.7 g of azobisisoheptanenitrile initiator, and 2.0 g of alkyl aluminum activator into container B. After the addition is completed, the reaction solution B is obtained after stirring.

[0040] Step 5: Weigh 50g of reaction liquid A and 50g of reaction liquid B, and quickly inject them into the mold through a single screw. The reaction injection molding temperature is 75°C, the holding pressure is 0.6 MPa, and the holding time is 10 minutes. Take out the sample for performance testing. The sample is a flame-retardant polydicyclopentadiene composite material.

[0041] Example 4 Reference Figure 1 , a flame retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network and a preparation method thereof, the specific steps are as follows: Step 1: Weigh 40 g of vinyltrimethoxysilane, 800 g of n-butyl methacrylate and 10 g of p-hydroxyanisole, add into a 2000 mL three-necked flask, introduce nitrogen, heat to 60° C., add dropwise 8 g of pentaerythritol triacrylate, heat to 80° C., continue the reaction for 1 h, and obtain a silicone-modified acrylate compound.

[0042] Step 2: Weigh 800 g of dicyclopentadiene and 100 g of butadiene rubber, add them into a 2000 mL three-necked flask, heat to 95° C., and stir for 30 min to obtain thickened dicyclopentadiene.

[0043] Step 3: Under the protection of high-purity nitrogen, 160 g of organosilicon-modified acrylate compound, 2.5 g of tungsten hexachloride catalyst and 800 g of chloroform solvent are added to container A. After the addition is completed, reaction solution A is obtained after stirring.

[0044] Step 4: Under the protection of high-purity nitrogen, add 115 g of thickening dicyclopentadiene, 0.8 g of azobisisoheptanenitrile initiator, and 2.5 g of alkyl aluminum activator into container B. After the addition is completed, the reaction solution B is obtained after stirring.

[0045] Step 5: Weigh 60g of reaction liquid A and 40g of reaction liquid B, and quickly inject them into the mold through a single screw. The reaction injection molding temperature is 75°C, the holding pressure is 0.6 MPa, and the holding time is 10 minutes. Take out the sample for performance testing. The sample is a flame-retardant polydicyclopentadiene composite material.

[0046] Example 5 Reference Figure 1 , a flame retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network and a preparation method thereof, the specific steps are as follows: Step 1: Weigh 50g of tetramethoxysilane, 1000g of methyl methacrylate and 10g of p-hydroxyanisole, add into a 2000mL three-necked flask, introduce nitrogen, heat to 60°C, add 10g of pentaerythritol triacrylate dropwise, heat to 80°C, continue the reaction for 1h, and obtain a silicone-modified acrylate compound.

[0047] Step 2: Weigh 1000 g of dicyclopentadiene and 100 g of butadiene rubber, add into a 2000 mL three-necked flask, heat to 95° C., and stir for 30 min to obtain thickened dicyclopentadiene.

[0048] Step 3: Under the protection of high-purity nitrogen, 200 g of organosilicon-modified acrylate compound, 3.0 g of tungsten hexachloride catalyst and 1000 g of chloroform solvent are added into container A. After the addition is completed, reaction solution A is obtained after stirring.

[0049] Step 4: Under the protection of high-purity nitrogen, add 120 g of thickening dicyclopentadiene, 1.0 g of dibenzoyl peroxide initiator, and 3.0 g of alkyl aluminum activator into container B. After the addition is completed, the reaction solution B is obtained after stirring.

[0050] Step 5: Weigh 70g of reaction liquid A and 30g of reaction liquid B, and quickly inject them into the mold through a single screw. The reaction injection molding temperature is 75°C, the holding pressure is 0.6 MPa, and the holding time is 10 minutes. Take out the sample for performance testing. The sample is a flame-retardant polydicyclopentadiene composite material.

[0051] Comparative Example 1 A polydicyclopentadiene composite material and a preparation method thereof, the specific steps are as follows: Step 1: Weigh 500 g of dicyclopentadiene and 100 g of butadiene rubber, add them into a 2000 mL three-necked flask, heat to 95° C., and stir for 30 minutes to obtain thickened dicyclopentadiene.

[0052] Step 2: Under the protection of high-purity nitrogen, 100 g of methyl methacrylate, 1 g of tungsten hexachloride catalyst and 500 g of methyl ethyl ketone solvent are added into container A. After the addition is completed, reaction solution A is obtained after stirring.

[0053] Step 3: Under the protection of high-purity nitrogen, add 100 g thickening dicyclopentadiene, 0.5 g potassium persulfate initiator, and 1 g alkyl aluminum activator into container B. After the addition is completed, the reaction solution B is obtained after stirring.

[0054] Step 4: Weigh 30g of reaction liquid A and 70g of reaction liquid B, and quickly inject them into the mold through a single screw. The reaction injection molding temperature is 75°C, the holding pressure is 0.6 MPa, and the holding time is 10 minutes. Take out the sample for performance testing. The sample is a polydicyclopentadiene composite material.

[0055] Comparative Example 2 A polydicyclopentadiene composite material and a preparation method thereof, the specific steps are as follows: Step 1: Weigh 20 g of tetramethoxysilane, 600 g of ethyl methacrylate and 10 g of p-hydroxyanisole, add into a 2000 mL three-necked flask, introduce nitrogen, heat to 60° C., dropwise add 6 g of pentaerythritol triacrylate, heat to 80° C., continue the reaction for 1 h, and obtain a silicone-modified acrylate compound.

[0056] Step 2: Weigh 600 g of dicyclopentadiene and 100 g of butadiene rubber, add them into a 2000 mL three-necked flask, heat to 95° C., and stir for 30 minutes to obtain thickened dicyclopentadiene.

[0057] Step 3: Under the protection of high-purity nitrogen, 120 g of an organosilicon-modified acrylate compound, 1.5 g of a tungsten tetrabromide catalyst and 600 g of a dichloromethane solvent are added to a container A. After the addition is completed, a reaction solution A is obtained after stirring.

[0058] Step 4: Under the protection of high-purity nitrogen, 105 g of thickening dicyclopentadiene, 0.6 g of dibenzoyl peroxide initiator, and 1.5 g of alkyl aluminum activator are added to container B. After the addition is completed, reaction solution B is obtained after stirring.

[0059] Step 5: Weigh 40g of reaction solution A and 60g of reaction solution B, place them in a 500mL beaker and stir them evenly, quickly pour them into a mold for casting, and take out the sample for performance testing. The sample is the polydicyclopentadiene composite material.

[0060] Comparative Example 3 A polydicyclopentadiene composite material and a preparation method thereof, the specific steps are as follows: Step 1: Weigh 30 g of trimethylmethoxysilane, 700 g of styrene and 10 g of p-hydroxyanisole, add into a 2000 mL three-necked flask, introduce nitrogen, heat to 60° C., dropwise add 7 g of pentaerythritol triacrylate, heat to 80° C., continue the reaction for 1 h, and obtain a silicone-modified styrene compound.

[0061] Step 2: Weigh 700 g of dicyclopentadiene and 100 g of butadiene rubber, add them into a 2000 mL three-necked flask, heat to 95° C., and stir for 30 minutes to obtain thickened dicyclopentadiene.

[0062] Step 3: Under the protection of high-purity nitrogen, 140 g of organosilicon-modified styrene compound, 2.0 g of tungsten boride catalyst and 700 g of chloroform solvent are added to container A. After the addition is completed, reaction solution A is obtained after stirring.

[0063] Step 4: Under the protection of high-purity nitrogen, add 110 g of thickening dicyclopentadiene, 0.7 g of azobisisoheptanenitrile initiator, and 2.0 g of alkyl aluminum activator into container B. After the addition is completed, the reaction solution B is obtained after stirring.

[0064] Step 5: Weigh 50g of reaction liquid A and 50g of reaction liquid B, and quickly inject them into the mold through a single screw. The reaction injection molding temperature is 75°C, the holding pressure is 0.6 MPa, and the holding time is 10 minutes. Take out the sample for performance testing. The sample is a polydicyclopentadiene composite material.

[0065] 2. Evaluating performance The evaluation results of the polydicyclopentadiene composite materials of Examples 1-5 and Comparative Examples 1-3 are shown in Table 1.

[0066] Table 1 Evaluation results of polymers obtained in various examples and comparative examples

[0067] Among them, in Table 1: Tensile strength is tested according to ISO 527-1:2019.

[0068] The notched impact strength is tested according to ISO 180-2019 Izod beam notched impact strength at room temperature.

[0069] Heat distortion temperature is tested according to ISO 75-1-2013.

[0070] The oxygen index is tested according to GB-T 2406-1993.

[0071] Analysis: It can be seen from Example 1 and Comparative Example 1 that the organic silicon modified acrylate compound intrinsic flame retardant of the present invention has a good flame retardant effect, and the organic silicon is embedded in the polymer in the form of a covalent bond, so that the flame retardant composite material has excellent flame retardant properties while maintaining excellent mechanical strength. It can be seen from Example 2 and Comparative Example 2 that compared with the casting molding process, the cross-linked interpenetrating network structure formed by the reaction injection molding process helps to improve the mechanical strength of the composite material, and the surface of the composite material is more likely to form a dense ceramic carbon layer during the combustion process, and the flame retardant effect is better; It can be seen from Example 3 and Comparative Example 3 that the synergistic enhancement effect of acrylate and dicyclopentadiene is better than that of styrene, and the resulting composite material has higher mechanical strength, heat resistance and flame retardant properties. In summary, the flame retardant polydicyclopentadiene composite material with a cross-linked interpenetrating network prepared by the present invention has excellent mechanical strength, impact toughness, heat resistance and flame retardant properties, and has good application prospects.

[0072] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms should not be understood as necessarily being directed to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine different embodiments or examples described in this specification.

[0073] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A method for preparing a polydicyclopentadiene composite material, characterized in that: The steps include: Preparation of organosilicon-modified acrylate compound: siloxane, acrylate compound and p-hydroxyanisole are added to a flask in sequence, nitrogen is introduced, the temperature is increased, pentaerythritol triacrylate is added dropwise, the temperature is increased, and the reaction is continued to obtain an organosilicon-modified acrylate compound; Dicyclopentadiene thickening treatment: Dicyclopentadiene and butadiene rubber are heated and stirred to obtain thickened dicyclopentadiene; Preparation of reaction solution A: under the protection of high-purity nitrogen, add the organosilicon-modified acrylate compound, the catalyst and the solvent into container A, and after the addition is completed, stir to obtain reaction solution A; Preparation of reaction solution B: under the protection of high-purity nitrogen, thickening dicyclopentadiene, initiator, and alkyl aluminum activator are added to container B. After the addition is completed, the reaction solution B is obtained after stirring; Molding: The reaction liquid A and the reaction liquid B are subjected to reaction injection molding to obtain a polydicyclopentadiene composite material.

2. The method for preparing a polydicyclopentadiene composite material according to claim 1, characterized in that: The step of preparing the organosilicon-modified acrylate compound also includes: adding siloxane, acrylate compound and p-hydroxyanisole into a three-necked flask in sequence, introducing nitrogen, heating to 30-80° C., dropping pentaerythritol triacrylate, heating to 50-100° C., and continuing the reaction for 0.5-3 hours to obtain the organosilicon-modified acrylate compound.

3. The method for preparing a polydicyclopentadiene composite material according to claim 1, characterized in that: In the preparation of the organosilicon-modified acrylate compound, the siloxane includes one or more of vinyl trimethoxysilane, tetramethoxysilane, and trimethylmethoxysilane; the acrylate compound includes one or more of methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate; the mass ratio of the siloxane, the acrylate compound, and p-hydroxyanisole is 1-5:50-100:1; and the added amount of pentaerythritol triacrylate is 5-10g.

4. The method for preparing a polydicyclopentadiene composite material according to claim 1, characterized in that: The step of thickening treatment of dicyclopentadiene also includes: heating dicyclopentadiene and butadiene rubber to 60-120° C. and stirring for 10-40 minutes to obtain thickened dicyclopentadiene.

5. The method for preparing a polydicyclopentadiene composite material according to claim 1, characterized in that: In the dicyclopentadiene thickening treatment, the mass ratio of dicyclopentadiene to butadiene rubber is 5-10:

1.

6. The method for preparing a polydicyclopentadiene composite material according to claim 1, characterized in that: In the preparation of reaction solution A, the catalyst includes one or more of tungsten hexachloride, tungsten tetrabromide, and tungsten boride; the solvent includes one or more of methyl ethyl ketone, dichloromethane, and chloroform; the mass ratio of the organosilicon-modified acrylate compound, the catalyst, and the solvent is 10-20:0.1-0.3:50-100.

7. The method for preparing a polydicyclopentadiene composite material according to claim 1, characterized in that: In the preparation of reaction solution B, the initiator includes one or more of potassium persulfate, dibenzoyl peroxide, and azobisisoheptanenitrile; the mass ratio of thickening dicyclopentadiene, initiator, and alkyl aluminum is 100-120:0.5-1:1-3.

8. The method for preparing a polydicyclopentadiene composite material according to claim 1, characterized in that: The molding step also includes: rapidly injecting the reaction liquid A and the reaction liquid B into the mold through a single screw, the reaction injection molding temperature is 60-80°C, the holding pressure is 0.1-1 MPa, and the holding time is 5-30 minutes to obtain a polydicyclopentadiene composite material.

9. The method for preparing a polydicyclopentadiene composite material according to claim 1, characterized in that: During molding, the mass ratio of reaction liquid A to reaction liquid B is 3-7:7-3.

10. A flame retardant polydicyclopentadiene composite material having a cross-linked interpenetrating network, characterized in that: The polydicyclopentadiene composite material is prepared according to the preparation method of any one of claims 1 to 9.

Images