WO2024041220A1

WO2024041220A1 - Polycarbonate composite material, preparation method therefor, and use thereof

Info

Publication number: WO2024041220A1
Application number: PCT/CN2023/105138
Authority: WO
Inventors: 刘春艳; 王慧珊
Original assignee: 上海中镭新材料科技有限公司
Priority date: 2022-08-24
Filing date: 2023-06-30
Publication date: 2024-02-29
Also published as: CN115260731A

Abstract

Provided are a polycarbonate composite material, a preparation method therefor, and use thereof. The polycarbonate composite material comprises, in parts by weight: 30-90 parts of polycarbonate, 0.5-5 parts of an amino-containing compatilizer, 2-10 parts of a plasticizer, 2-4 parts of a phosphorus-based flame retardant, and 2-8 parts of a silicon-based flame retardant. The amino-containing compatilizer includes a nylon compatilizer. The plasticizer includes a plasticizer containing an m-benzene structure. According to the polycarbonate composite material, the specific type of compatilizer and plasticizer are added, and meanwhile, the phosphorus-based flame retardant and the silicon-based flame retardant synergistically retard flame, such that the polycarbonate composite material has excellent flame retardance, low smoke density and smoke release amount, low heat release rate and low smoke toxicity while taking the mechanical property into consideration, and thus is suitable for the fields of rail transit, aerospace, and the like.

Description

Polycarbonate composite materials and their preparation methods and applications

Technical field

This application belongs to the technical field of polycarbonate materials, and specifically relates to a polycarbonate composite material and its preparation method and application.

Background technique

At present, rail transit construction at home and abroad is developing rapidly, especially my country's rail transit technology. The operating lines are constantly growing, and the number of freight and passenger transportation is increasing year by year. It has become an important supporting force in the construction of the Beijing-Tianjin-Hebei, Yangtze River Delta, and Guangdong-Hong Kong-Macao Greater Bay Area. In relatively closed spaces with dense crowds and small space, including rail transit, cargo airlines, etc., once combustion occurs, oxygen will be quickly consumed, heat and toxic flammable gases will be released, which will greatly endanger people's lives and property safety. As people's demand for travel and transportation increases, it has become a top priority to develop a material with low heat release and low smoke density to meet the needs of rail transportation and aerospace.

The UL94 standard developed by Underwriters Laboratories is currently an important standard for evaluating the fire performance of materials in the conventional field. This system is mainly used to evaluate the flammability of the material itself. However, it is not suitable for special applications, such as air cabins, ship cabins, and rail land transportation that are small and tightly packed with people concentrated. For aerospace, the heat release standard FAR25.853 for materials has been established; for rail transit, the European Union has launched a unified fire protection standard EN45545, which plays an important role in reducing casualties and losses caused by combustion in aerospace cabins and rail transit.

Polycarbonate (PC) is a thermoplastic engineering resin with excellent comprehensive properties. It has excellent mechanical properties, heat resistance, dielectric properties and good processability. It is widely used in electronic appliances, automotive industry, aerospace, etc. field. However, polycarbonate itself has average flame retardancy and can only meet the UL94V-2 standard and cannot meet the EN45545 standard. Therefore, PC needs to be modified to improve its flame retardant performance.

Modification methods commonly used in related technologies include chemical modification and physical modification; chemical modification introduces flame-retardant functional groups through chemical reactions, such as halogen, phosphate, siloxane and other structures; however, the copolymerization method is more complex and costly. High, so physical modification is often used; physical modification enhances the flame retardancy of the mixture by adding flame retardants. For example, patent CN104830041A discloses a low heat release polycarbonate material. The polycarbonate material is compounded with a brominated flame retardant, semi-aromatic polyester and silicone polycarbonate to meet the flame retardant standards of aerospace. , however, brominated flame retardants will release toxic gases during the combustion process, which poses safety issues.

CN108047674A discloses a low-gloss, low-smoke, halogen-free flame-retardant polycarbonate composite material, which uses a sulfonate flame retardant, a polysiloxane flame retardant and an epoxy reactive compatibilizer to make the composite material The smoke density is low. However, the composite material has poor impact resistance.

In addition, the composite materials disclosed in the related art that meet the EU EN45545HL3 standard, such as the materials disclosed in CN112409770A, CN105431486A and CN105209312A, have high costs and are not suitable for mass production.

Therefore, developing a polycarbonate composite material with low heat release, low smoke density, good flame retardancy, mechanical properties, and low cost, suitable for aerospace and rail transit fields, is an urgent need in this field. technical issues.

Contents of the invention

The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.

The purpose of this application is to provide a polycarbonate composite material and its preparation method and application. The polycarbonate composite material is made by adding specific types of compatibilizers and plasticizers, and at the same time, the phosphorus-based flame retardant and the silicon-based flame retardant are synergistically flame retardant, so that the polycarbonate composite material has both mechanical properties and At the same time, It has excellent flame retardant properties, low smoke density and smoke release, slow heat release rate, and low smoke toxicity. It is suitable for rail transportation, aerospace and other fields.

To achieve this purpose, this application adopts the following technical solutions:

In the first aspect, embodiments of the present application provide a polycarbonate composite material. In parts by weight, the polycarbonate composite material includes 30 to 90 parts of polycarbonate, 0.5 to 5 parts of amino-containing compatibilizer, 2 to 10 parts of plasticizer, 2 to 4 parts of phosphorus flame retardant and 2 to 8 parts of silicon flame retardant; the amino-containing compatibilizer includes nylon compatibilizer; the plasticizer includes an iso-phenylene structure of plasticizer.

In the embodiments of this application, the iso-phenylene structure of the polycarbonate material is constructed by adding a plasticizer containing an iso-phenylene structure into the polycarbonate material. At the same time, a compatibilizer containing an amino group is added, and the amino group interacts with the polycarbonate. The terminal hydroxyl reaction consumes the easily broken ester groups of polycarbonate, and at the same time improves the dispersion of plasticizers containing m-phenylene structures in polycarbonate, which can cause polycarbonate to form a polyphenyl ring fused ring structure during the combustion process. , easy to form carbon; further, through the synergistic flame retardancy of phosphorus-based flame retardants and silicon-based flame retardants, carbon formation is promoted, thereby reducing smoke density and heat release rate, and has excellent flame retardant properties.

In one embodiment, the polycarbonate composite material includes 30 to 90 parts by weight of polycarbonate, such as 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, and 70 parts. , 72 copies, 74 copies, 75 copies, 76 copies, 78 copies, 80 copies, 82 copies, 84 copies, 86 copies, 88 copies, etc.

In one embodiment, the polycarbonate composite material includes 0.5 to 5 parts by weight of the amino-containing compatibilizer, for example, it can be 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4 parts, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, etc.

In one embodiment, the polycarbonate composite material includes 2 to 10 parts of plasticizer in parts by weight, such as 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or 5.5 parts. , 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, etc.

In the embodiments of this application, when the amount of the plasticizer is too small, the carbon-forming effect is poor; when the amount is too much, it is easy to precipitate and the flame retardant performance is poor.

In one embodiment, the polycarbonate composite material includes 2 to 4 parts by weight of phosphorus-based flame retardant, for example, it can be 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, etc.

In one embodiment, the polycarbonate composite material includes 2 to 8 parts by weight of silicone flame retardant, for example, it can be 2.5 parts, 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, 7.8 parts, etc.

In one embodiment, the polycarbonate composite material includes 70 to 90 parts by weight of polycarbonate.

In one embodiment, under the condition of 300°C and 1.2kg, the melt flow rate of the polycarbonate is 5-40g/min, for example, it can be 10g/min, 12g/min, 14g/min, 16g/min. , 18g/min, 20g/min, 22g/min, 24g/min, 26g/min, 28g/min, 30g/min, 32g/min, 34g/min, 36g/min, 38g/min, etc.

In one embodiment, the nylon compatibilizer includes any one or a combination of at least two of PA6, PA66, PAII, PA12, PA46, PA610, PA612 or PA1010, preferably at least one of PA6, PA66 or PA1010. A sort of.

In one embodiment, the plasticizer includes an isophthalate plasticizer.

In one embodiment, the isophthalate plasticizer includes diphenyl isophthalate.

In the embodiments of this application, the best effect is achieved when a combination of PA6 and diphenyl isophthalate is used as the amino-containing compatibilizer and plasticizer.

In one embodiment, the mass ratio of the amino-containing compatibilizer to the plasticizer is (0.8-2):1, for example, it can be 0.85:1, 0.9:1, 0.95:1, 1:1, 1.1: 1. 1.2:1, 1.3:1, 1.4:1, 1.45:1, 1.5:1, 1.55:1, 1.6:1, 1.65:1, 1.7:1, 1.75:1, 1.8:1, 1.85:1, 1.9:1, 1.95:1, etc.

In the embodiments of this application, the mass ratio of the amino-containing compatibilizer to the plasticizer has a good flame retardant effect within a specific range.

In one embodiment, the phosphorus-based flame retardant includes any one or a combination of at least two of ammonium polyphosphate, ammonium phosphate salts, phosphate ester flame retardants or phosphite ester flame retardants, preferably Phosphate ester flame retardant.

In one embodiment, the phosphate flame retardant includes resorcinol bis(diphenyl phosphate).

In one embodiment, the mass ratio of the phosphorus-based flame retardant to the silicon-based flame retardant is (0.8-2):1, for example, it can be 0.85:1, 0.9:1, 0.95:1, 1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, etc.

In the embodiments of the present application, the phosphorus-based flame retardant and the silicon-based flame retardant synergize within a specific ratio to further improve the flame retardant performance.

In one embodiment, the silicone-based flame retardant includes a combination of silica and silicone flame retardants.

In one embodiment, the mass ratio of silica to silicone flame retardant is (0.2-3):1, for example, it can be 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7: 1. 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 2:1, 2.5:1, 2.8:1, etc., preferably (0.4~2):1.

In the embodiments of this application, the silicon-based flame retardant is compounded with silicone flame retardant and silica, which can further promote carbon formation and improve the flame retardant performance; when the amount of silica is too small, the carbon formation effect is poor ; When the dosage is too much, the mechanical properties will be poor.

In one embodiment, the particle size of the silica is 15-25nm, for example, it can be 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, 23nm, 24nm, etc.

In one embodiment, the silicone flame retardant includes a silicone polymer.

In the embodiments of this application, silicone polymer is used as the organic silicon, which can penetrate into the polymer network and achieve The structure of the current cross-linking mechanism is not easy to precipitate to the surface of the substrate, and the synergistic effect with nano-silica makes it easier to form carbon during the combustion process, further reducing the release of harmful gases such as smoke.

In one embodiment, the polycarbonate composite material also includes 0.1 to 1 part of coupling agent in parts by weight, for example, it can be 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part parts, 0.9 parts, etc.

In one embodiment, the coupling agent includes a silane coupling agent and/or a titanate coupling agent.

In one embodiment, the silane coupling agent includes γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane Silane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-amine Ethyl-γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, polyaminopropyltriethoxysilane Any one or a combination of two or more of alkyltrialkoxysilane and anilinemethyltrimethoxysilane.

In one embodiment, the polycarbonate composite material further includes 0.5 to 2 parts by weight of an antioxidant, such as 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, etc.

In one embodiment, the antioxidant includes any one or at least two of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant B215, antioxidant 2246 or antioxidant 264 The combination.

In one embodiment, the polycarbonate composite material also includes 0.5 to 2 parts by weight of an anti-drip agent, such as 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, etc. .

In one embodiment, the anti-drip agent includes a fluoropolymer.

In one embodiment, the polycarbonate composite material further includes 0.5 to 2 parts by weight of toner, such as 0.8 parts, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, etc.

In this application, the toner is not limited too much, and the appropriate toner can be selected according to actual needs.

In a second aspect, embodiments of the present application provide a polycarbonate composite material according to the first aspect The preparation method includes the following steps:

Polycarbonate, amino-containing compatibilizer, plasticizer, phosphorus flame retardant and silicon flame retardant are blended and extruded to obtain the polycarbonate composite material.

In one embodiment, the mixed materials further include any one or a combination of at least two of coupling agents, antioxidants, anti-drip agents or toners.

In one embodiment, the blending time is 5 to 10 minutes, for example, it can be 6 minutes, 7 minutes, 8 minutes, 9 minutes, etc.

In one embodiment, the blending temperature is 10-50°C, for example, it can be 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, etc.

In one embodiment, the extrusion equipment includes a twin-screw extruder.

In one embodiment, the extrusion temperature is 230-290°C, for example, it can be 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, etc.

In one embodiment, the extrusion speed is 300 to 1000 rpm, for example, it can be 350 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, 650 rpm, 700 rpm, 750 rpm, 800 rpm, 850 rpm, 900 rpm, 950 rpm, etc.

As an optional technical solution for the embodiments of this application, the preparation method includes: combining polycarbonate, amino-containing compatibilizer, plasticizer, phosphorus-based flame retardant, silicon-based flame retardant and optional coupling agent , antioxidant, anti-drip agent or toner are blended for 5 to 10 minutes at 10 to 50°C, and extruded using a twin-screw machine at 230 to 290°C and 300 to 1000 rpm to obtain the polycarbonate. Ester composite material.

In a third aspect, embodiments of the present application provide an application of the polycarbonate composite material as described in the first aspect in preparing interior and exterior decorative parts of vehicles.

The numerical range described in this application not only includes the point values listed above, but also includes any point values between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, this application will not be exhaustive. List specific point values included in the stated range.

Compared with the existing technology, the beneficial effects of this application are:

The polycarbonate composite material provided in this application is made by adding specific types of compatibilizers and plasticizers, and at the same time, the phosphorus-based flame retardant and the silicon-based flame retardant are synergistically flame retardant, so that the polycarbonate composite material can While taking into account mechanical properties, it has excellent flame retardant properties, low smoke density and smoke release, slow heat release rate, and low smoke toxicity; the normal temperature notched impact strength of the polycarbonate composite material is ≥730J/m, and the tensile strength ≥58MPa, heat distortion temperature ≥95℃, oxygen index ≥31%, average maximum heat release rate ≤200KW/m ² , smoke density ≤300kg/m ^-3 , 4min cumulative smoke density ≤490kg/m ^-3 , toxic gas concentration ≤ 0.16.

Detailed ways

The technical solutions of the present application will be further described below through specific implementations. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

The materials used in the examples and comparative examples of this application are as follows (not limited to the following raw materials):

Silicone flame retardant: American General Company SFR-100;

Toner: commercially available.

Example 1

This embodiment provides a polycarbonate composite material. In parts by weight, the polycarbonate composite material includes 80 parts of polycarbonate (Bayer PC6555, Germany), 5 parts of PA6 (Sinopec Baling BL3280H), and 5 parts of isophthalic acid. Diphenyl dicarboxylate, 4 parts resorcinol bis(diphenyl phosphate), 2 parts silicone flame retardant, 1 part silica, 0.5 parts γ-methacryloyloxypropyltrimethoxy Silane, 1 part antioxidant 1010, 0.5 parts anti-drip agent K-PT200 and 1 part toner.

This embodiment provides a method for preparing the polycarbonate composite material. The preparation method includes the following steps:

Polycarbonate, 110℃, drying material for 6h, nylon 6, 80℃, drying material for 6h;

Combine polycarbonate, PA6, diphenyl isophthalate, resorcinol bis(diphenylphosphate), silicone flame retardant, silica, γ-methacryloyloxypropyltrimethoxy Based on silane, antioxidant 1010, anti-drip agent K-PT200 and toner, in the mixer, after blending at medium speed for 5 minutes, use a twin-screw extruder to extrude at 280°C and 600rpm to obtain the above Polycarbonate composite.

Example 2

This embodiment provides a polycarbonate composite material. In parts by weight, the polycarbonate composite material includes 88 parts of polycarbonate (Bayer PC6265 of Germany), 3 parts of PA66 (DuPont 70G30L of the United States), and 3.75 parts of isophthalene. Diphenyl formate, 3 parts of resorcinol bis(diphenyl phosphate), 1.3 parts of silicone flame retardant, 2.45 parts of silica, 0.5 parts of γ-glycidoxypropyltriethoxysilane, 0.5 parts of antioxidant 168, 0.5 parts of anti-drip agent TF-1645 (3M) and 0.5 parts of toner.

This embodiment provides a method for preparing the polycarbonate composite material. The specific steps are the same as those in Embodiment 1.

Example 3

This embodiment provides a polycarbonate composite material. In parts by weight, the polycarbonate composite material includes 75 parts of polycarbonate (Bayer PC2205, Germany), 5 parts of PA1010 (DuPont LC1000BK385), and 2.5 parts of isophthalic acid. Diphenyl ester, 4 parts resorcinol bis (diphenyl phosphate), 1 part silicone flame retardant, 1.5 parts silica, 0.5 parts γ-aminopropylmethyldiethoxysilane, 1.5 parts Antioxidant 264, 1.5 parts anti-drip agent K-PT202 and 0.5 parts toner.

Example 4

This embodiment provides a polycarbonate composite material, which is different from Embodiment 1 only in that the The proportion of silicone flame retardant is 3 parts, and there is no silica. The other components, dosage and preparation method are the same as in Example 1.

Example 5

This embodiment provides a polycarbonate composite material, which is different from Example 1 only in that the amount of silica is 5 parts, and other components, amounts and preparation methods are the same as Example 1.

Example 6

This embodiment provides a polycarbonate composite material. The only difference from Example 1 is that the polycarbonate composite material contains 2 parts of resorcinol bis(diphenyl phosphate), and the other components The ingredients, dosage and preparation method are the same as those in Example 1.

Example 7

This embodiment provides a polycarbonate composite material, which is different from Example 1 only in that the polycarbonate composite material contains 2 parts of resorcinol bis(diphenyl phosphate) and silicone The proportion of flame retardant is 4 parts, and other components, dosage and preparation method are the same as in Example 1.

Example 8

This embodiment provides a polycarbonate composite material, which is different from Example 1 only in that the resorcinol bis(diphenyl phosphate) is replaced by an equal weight part of resorcinol bis(diphenyl phosphate). phenyl phosphate), other components, dosage and preparation method are the same as in Example 1.

Example 9

This embodiment provides a polycarbonate composite material, which is different from Example 1 only in that the polycarbonate composite material contains 2 parts of diphenyl isophthalate, and other components, dosage and preparation The methods are all the same as in Example 1.

Example 10

This embodiment provides a polycarbonate composite material, which is different from Embodiment 1 only in that the The proportion of diphenyl isophthalate in the polycarbonate composite material is 8 parts, and the other components, dosage and preparation method are the same as in Example 1.

Example 11

This embodiment provides a polycarbonate composite material, which is different from Example 1 only in that the proportion of PA6 in the polycarbonate composite material is 2 parts, and other components, dosages and preparation methods are the same as those in Example 1. 1 is the same.

Example 12

This embodiment provides a polycarbonate composite material, which is different from Example 1 only in that PA6 in the polycarbonate composite material is replaced by equal weight parts of PA12 (Evonik Degussa L2140, Germany), and the other The components, dosage and preparation method are the same as in Example 1.

Comparative example 1

This comparative example provides a polycarbonate composite material. The difference from Example 1 is that the composite material includes 97 parts of polycarbonate, without PA6, diphenyl isophthalate, resorcin bis(di Phenyl phosphate), silicone flame retardant and silica, other components, dosage and preparation method are the same as in Example 1.

Comparative example 2

This comparative example provides a polycarbonate composite material. The difference from Example 1 is that the composite material includes 90 parts of polycarbonate, without PA6 and diphenyl isophthalate, and other components, dosage and preparation The methods are all the same as in Example 1.

Comparative example 3

This comparative example provides a polycarbonate composite material. The difference from Example 1 is that the composite material includes 85 parts of polycarbonate without PA6. Other components, dosages and preparation methods are the same as Example 1.

Comparative example 4

This comparative example provides a polycarbonate composite material, which is different from Example 1 only in that the number of parts of resorcinol bis(diphenyl phosphate) is 12 parts, and other components, dosage and preparation The methods are all the same as in Example 1.

Comparative example 5

This comparative example provides a polycarbonate composite material, which is different from Example 1 only in that the diphenyl isophthalate is replaced by diphenyl terephthalate in equal parts by weight, and the other components are: The dosage and preparation method are the same as in Example 1.

Performance Testing

(1) Impact strength: Tested in accordance with ASTM D256-2010E1 standard under normal temperature conditions;

(2) Tensile strength: tested according to ISO 527 method;

(3) Flexural modulus: tested according to ISO 178 method;

(4) Heat distortion temperature: tested according to ISO 75 method

(5) Flame retardancy: evaluated according to UL94 flame retardant grade;

(6) Average maximum heat release rate (MARHE): tested in accordance with EN ISO5660-1 method;

(7) Smoke density Ds-4: Tested according to EN ISO5659-2 method;

(8) 4min cumulative smoke density (VOF ₄ ): tested in accordance with the EN ISO5659-2 method;

(8) Toxic gas: tested according to EN ISO5659-2 method;

The specific test results are shown in Table 1:

Table 1

As can be seen from the above table, the polycarbonate composite material provided by the present application is flame retardant by adding specific types of compatibilizers and plasticizers, and at the same time, the phosphorus-based flame retardant and the silicon-based flame retardant are synergistically flame retardant, making the polycarbonate composite material While taking into account mechanical properties, the polycarbonate composite material has excellent flame retardant properties, low smoke density and smoke release, slow heat release rate, and low toxicity; it can be seen from Examples 1 to 3 that the polycarbonate composite material The normal temperature notched impact strength of the material is 740~750J/m, the tensile strength reaches 60~62MPa, the flexural modulus is 2780~2850MPa, the thermal deformation temperature is 100~101℃, the oxygen index reaches 48~49%, and the average maximum heat release rate is only 85～86KW/m ² , smoke density is 120～121kg/m ^-3 , cumulative smoke density in 4 minutes is 250～252kg/m ^-3 , toxic gas concentration is 0.1.

It can be seen from the comparison between Example 1 and Examples 4 to 8 that the flame retardant is not a specific combination and ratio, and the flame retardant performance of the polycarbonate composite material is poor; from the comparison between Example 1 and Examples 9 to 12 It can be seen that when the compatibilizer and plasticizer are not in a specific combination and ratio, the polycarbonate composite material has poor flame retardant properties; from a comparison between Example 1 and Comparative Examples 1 to 3, it can be seen that the polycarbonate composite material has poor flame retardancy. When there is no nylon compatibilizer, plasticizer or flame retardant in the ester composite material, the polycarbonate composite material has poor flame retardant performance, low smoke density and slow heat release rate; from Example 1 and Comparative Example 4 and 5 Comparatively, it can be seen that the proportion of the phosphorus flame retardant is too The flame retardant effect is poor when plasticizers containing p-benzene structure are used.

To sum up, the polycarbonate composite material provided in this application adds specific types of compatibilizers and plasticizers, and at the same time uses phosphorus-based flame retardants and silicon-based flame retardants to synergistically flame retardant, making the polycarbonate Ester composite materials not only take into account mechanical properties, but also have excellent flame retardant properties, low smoke density and smoke release, slow heat release rate, and low toxicity. They are suitable for rail transportation, aerospace and other fields.

The above-mentioned specific embodiments further describe the purpose, technical solutions and beneficial effects of the present application in detail. It should be understood that the above-mentioned are only specific embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of this application shall be included in the protection scope of this application.

Claims

A polycarbonate composite material, in parts by weight, the polycarbonate composite material includes 30 to 90 parts of polycarbonate, 0.5 to 5 parts of amino-containing compatibilizer, 2 to 10 parts of plasticizer, 2 to 4 parts 2 parts of phosphorus flame retardant and 2 to 8 parts of silicon flame retardant;

The amino-containing compatibilizer includes nylon compatibilizer;

The plasticizer includes a plasticizer containing an iso-phenylene structure.
The polycarbonate composite material according to claim 1, wherein, in parts by weight, the polycarbonate composite material includes 70 to 90 parts of polycarbonate;

Optionally, under the conditions of 300° C. and 1.2 kg, the polycarbonate has a melt flow rate of 5 to 40 g/min.
The polycarbonate composite material according to claim 1 or 2, wherein the nylon compatibilizer includes any one or at least two of PA6, PA66, PAII, PA12, PA46, PA610, PA612 or PA1010. combination;

Optionally, the plasticizer includes isophthalate plasticizer;

Optionally, the isophthalate plasticizer includes diphenyl isophthalate;

Optionally, the mass ratio of the amino-containing compatibilizer to the plasticizer is (0.8-2):1.
The polycarbonate composite material according to claim 3, wherein the nylon compatibilizer includes at least one of PA6, PA66 or PA1010.
The polycarbonate composite material according to any one of claims 1 to 4, wherein the phosphorus-based flame retardant includes ammonium polyphosphate, ammonium phosphate salt, phosphate ester flame retardant or phosphite flame retardant. Any one or a combination of at least two of them;

Optionally, the phosphate flame retardant includes resorcinol bis(diphenyl phosphate);

Optionally, the mass ratio of the phosphorus-based flame retardant to the silicon-based flame retardant is (0.8~2):1;

Optionally, the silicone flame retardant includes a combination of silica and silicone flame retardants;

Optionally, the mass ratio of the silica to the silicone flame retardant is (0.2~3):1;

Optionally, the particle size of the silica is 15 to 25 nm;

Optionally, the silicone flame retardant includes a silicone polymer.
The polycarbonate composite material according to claim 5, wherein the phosphorus-based flame retardant is a phosphate ester flame retardant;

Optionally, the mass ratio of the silica to the silicone flame retardant is (0.4-2):1.
The polycarbonate composite material according to any one of claims 1 to 6, wherein, in parts by weight, the polycarbonate composite material further includes 0.1 to 1 part of coupling agent;

Optionally, the coupling agent includes silane coupling agent and/or titanate coupling agent;

Optionally, the silane coupling agent includes γ-methacryloyloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-aminoethyl -γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, polyaminoalkyl Any one or a combination of two or more of trialkoxysilane and anilinemethyltrimethoxysilane.
The polycarbonate composite material according to any one of claims 1 to 7, wherein, in parts by weight, the polycarbonate composite material further includes 0.5 to 2 parts of antioxidant;

Optionally, the antioxidant includes any one or a combination of at least two of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant B215, antioxidant 2246 or antioxidant 264. .
The polycarbonate composite material according to any one of claims 1 to 8, wherein, in parts by weight, the polycarbonate composite material further includes 0.5 to 2 parts of anti-drip agent;

Optionally, the anti-drip agent includes a fluoropolymer.
The polycarbonate composite material according to any one of claims 1 to 9, wherein, in parts by weight In total, the polycarbonate composite material also includes 0.5 to 2 parts of toner.
A method for preparing the polycarbonate composite material according to any one of claims 1 to 10, the preparation method comprising the following steps:

Polycarbonate, amino-containing compatibilizer, plasticizer, phosphorus flame retardant and silicon flame retardant are blended and extruded to obtain the polycarbonate composite material.
The preparation method according to claim 11, wherein the blended materials further include any one or a combination of at least two of coupling agents, antioxidants, anti-drip agents or toners;

Optionally, the blending time is 5 to 10 minutes;

Optionally, the blending temperature is 10 to 50°C;

Optionally, the extrusion equipment includes a twin-screw extruder;

Optionally, the extrusion temperature is 230 to 290°C;

Optionally, the extrusion speed is 300 to 1000 rpm.
The preparation method according to claim 11 or 12, wherein the preparation method includes the following steps:

Put polycarbonate, amino-containing compatibilizer, plasticizer, phosphorus-based flame retardant and silicon-based flame retardant as well as optional coupling agent, antioxidant, anti-drip agent or toner at 10~50℃ Blending for 5 to 10 minutes under the conditions, and extrusion using a twin-screw extruder at 230 to 290°C and 300 to 1000 rpm to obtain the polycarbonate composite material.
An application of the polycarbonate composite material according to any one of claims 1 to 10 in the preparation of interior and exterior decorative parts of vehicles.