Halogen-free flame-retardant PC composite material with high recovery ratio

Abstract

The invention relates to a halogen-free flame-retardant PC composite material with a high recovery ratio, which comprises the following components in parts by weight: 40-84 parts by mass of polycarbonate (PCR PC); 5-15 parts by mass of a flame retardant; 0.5-2 parts by mass of an anti-dripping agent; 0.2 to 0.8 part by mass of an antioxidant; 10 to 50 parts by mass of fiber; the material disclosed by the invention has the beneficial effects that the material does not contain dangerous halogen compounds, so that the risk of secondary pollution can be reduced when the material is recycled, a high-proportion recycled material (more than 50%) is used in the material, so that the material has higher environment-friendly performance, and the material disclosed by the invention takes PC as a main body, so that the material is more environment-friendly. 10-50% of GF filler is added, so that the glass fiber reinforced plastic not only has certain mechanical property and flame retardance (1.0 mm V-0), but also has higher thermal deformation temperature (more than 95 DEG C), and the application range of the glass fiber reinforced plastic can be effectively widened.

Description

[Technical field]

[0001] The invention relates to the technical field of polycarbonate composite materials, in particular to a halogen-free flame-retardant PC composite material with a high recycling ratio. [Background technology]

[0002] In the manufacturing process of many products, plastic materials are one of the most commonly used materials, and PC+GF (glass fiber) blend is a common plastic reinforcement material. This material has good mechanical properties, high wear resistance, high temperature resistance and dimensional stability, so it is widely used in various products, such as car accessories, computer casings, household appliances, toys, etc. However, since PC+GF blends contain halogen flame retardants, harmful substances may be released during the manufacturing, use and handling process, causing damage to the environment and human health.

[0003] In the past, a variety of technologies have been used to develop halogen-free flame-retardant PC+GF materials, such as the use of nitrogen-phosphorus flame retardants, silicates, boric acid, metal hydroxides, etc. However, these technologies have some disadvantages. For example, a large amount of flame retardants need to be added to achieve the flame retardant effect, which can easily lead to a decrease in the mechanical properties of the material, increase the material price and manufacturing cost, and may cause problems such as rough product surface or bubbles during processing.

[0004] In addition, in order to comply with environmental regulations, material recycling and reuse has become an important issue. Traditional PC+GF materials are difficult to be widely used because of their low recycling rate, poor physical properties, and impurities in the recycled materials. In addition, since the composition of PC+GF materials is relatively complex, including PC, glass fiber and other additives, they are easily disturbed by impurities during the recycling process, affecting the quality of the materials. Therefore, it is more difficult to achieve good flame retardancy when the product structure is approaching ultra-thin and lightweight.

[0005] In view of this, it is necessary to provide a halogen-free flame-retardant PC composite material with a high recycling rate to solve the above problems. [Summary of the invention]

[0006] The technical problem to be solved by the present invention is: since the PC+GF blend contains halogen flame retardants, harmful substances may be released during the manufacturing, use and processing, causing damage to the environment and human health. The currently manufactured halogen-free flame-retardant PC+GF materials require the addition of a large amount of flame retardants to achieve the flame retardant effect, but it is easy to cause the mechanical properties of the material to decrease, which increases the material price and manufacturing cost, and may cause problems such as rough product surface or bubbles during processing. In addition, the composition of PC+GF materials is relatively complex, including PC, glass fiber and other additives, so it is easily disturbed by impurities during the recycling process, affecting the quality of the material. Therefore, the present invention provides a halogen-free flame-retardant PC composite material with a high recycling ratio to solve the above problems.

[0007] The solution of the present invention to solve the technical problem is:

[0008] A halogen-free flame-retardant PC composite material with a high recycling ratio, characterized in that it includes the following components in parts by weight:

[0009] Polycarbonate (PCR PC), 40-84 parts by weight;

[0010] Flame retardant, 5 to 15 parts by weight;

[0011] Anti-dripping agent, 0.5 to 2 parts by mass;

[0012] Antioxidant, 0.2-0.8 parts by weight;

[0013] Fiber, 10-50 parts by weight;

[0014] Flow improver, 0.3 to 0.8 parts by mass.

[0015] The selected polycarbonate can be a combination of two or more of bisphenol A linear polycarbonate, polyester polycarbonate, silicone copolymer polycarbonate, cyclohexane bisphenol A polycarbonate, and polycarbonate synthesized from bisphenol TMC. The melt mass flow rate of the polycarbonate is MI = (3-25) g / 10min (300°C / 1.2kg), and the impact strength is IS = (15-72) kJ / m 2 , the weight average molecular weight is between 10000 and 50000, and the molecular weight distribution is between 1 and 3.

[0016] The selected polycarbonate (PC RPC) recycled components are 90-100%, and the types of polycarbonate can be one or more combinations of recycled water bottle materials, water bottle material fragments, recycled CD materials, CD fragments, recycled headlamp shell materials, headlamp shell fragments, electronic product recycled materials and their fragments.

[0017] The selected flame retardant can be a compound of two types of flame retardants selected from phosphate flame retardants, sulfonate flame retardants, organic silicon flame retardants and their derivative flame retardants.

[0018] The selected anti-dripping agent is a fluorine-based PTFE material, including a core-shell coated PTFE material and a non-coated PTFE (pure powder type) material.

[0019] The selected antioxidant composition is one or a combination of hindered phenols, hindered amines and phosphites.

[0020] The selected fibers may be one or more composite fibers such as glass fiber (GF), carbon fiber, mineral fiber, natural plant fiber and nylon fiber.

[0021] The selected flow modifier can be one or a combination of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, 1,3-phenylbis(2-oxazoline), 1,4-phenylbis(2-oxazoline), bis(2-oxazoline), diglycidyl ether cyclic diepoxide, diimide diepoxide, phthaloyl biscaprolactam, etc.

[0022] A product, characterized in that the product is prepared by adding GF filler and utilizing processing aids to obtain a halogen-free flame-retardant PC composite material with a high recycling ratio.

[0023] The beneficial effects of the present invention are:

[0024] 1. The material of the present invention does not contain dangerous halogen compounds, so the risk of secondary pollution can be reduced when it is recycled and reused.

[0025] 2. The material of the present invention uses a high proportion of recycled materials (>50%), making it more environmentally friendly.

[0026] 3. The material of the present invention is mainly composed of PC, to which 10-50% GF filler is added. In addition to having certain mechanical properties and flame retardancy (1.0mm V-0), it also has a higher heat deformation temperature (>95°C), which can effectively increase its application range. [Specific implementation method]

[0027] In order to further illustrate the technical means and effects adopted by the present invention, the embodiments of the present invention are described in detail below.

[0028] The present invention provides a halogen-free flame-retardant PC composite material with a high recycling ratio, which is characterized in that it comprises the following components in parts by weight:

[0029] Polycarbonate (PCR PC), 40-84 parts by weight;

[0030] Flame retardant, 5 to 15 parts by weight;

[0031] Anti-dripping agent, 0.5 to 2 parts by mass;

[0032] Antioxidant, 0.2-0.8 parts by weight;

[0033] Fiber, 10-50 parts by weight;

[0034] Flow improver, 0.3 to 0.8 parts by mass.

[0035] The selected polycarbonate can be a combination of two or more of bisphenol A linear polycarbonate, polyester polycarbonate, silicone copolymer polycarbonate, cyclohexane bisphenol A polycarbonate, and polycarbonate synthesized from bisphenol TMC. The melt mass flow rate of the polycarbonate is MI = (3 to 25) g / 10 min (300°C / 1.2 kg), and the impact strength is IS = (15 to 72) kJ / m 2 , the weight average molecular weight is between 10000 and 50000, and the molecular weight distribution is between 1 and 3.

[0036] Among them, the selected polycarbonate (PC RPC) recycled components are 90-100%, and the types of polycarbonate can be recycled water bottle materials, water bottle material fragments, recycled CD materials, CD fragments, recycled headlamp shell materials, headlamp shell fragments, electronic product recycled materials and their fragments, etc., or one or more combinations thereof.

[0037] The flame retardant selected can be a compound of two types of phosphate flame retardants (such as 1,3-phenylene (2,6-methylphenyl) phosphate tetraester, tetraphenyl bisphenol A diphosphate and its derivative flame retardants, tetraphenyl resorcinol diphosphate and its derivative flame retardants, triphenyl phosphate (TPP) flame retardant), sulfonate flame retardants (such as potassium benzenesulfonylbenzenesulfonate (KSS), potassium perfluorobutyl sulfonate (PPFBS), sodium 2,4,5-trichlorobenzenesulfonate (STB)), and silicone flame retardants (such as polysilicon borane and its derivative flame retardants, cross-linked polydimethylsiloxane (PDMS)) and its derivative flame retardants.

[0038] Wherein, the selected anti-dripping agent is a fluorine-based PTFE material, including core-shell coated PTFE material and non-coated PTFE (pure powder type) material.

[0039] The selected antioxidant is composed of one or a combination of hindered phenols, hindered amines and phosphites.

[0040] The selected fibers may be one or more composite fibers of glass fibers, carbon fibers, mineral fibers (such as silica, alumina, magnesium oxide, asbestos, etc.), natural plant fibers (such as straw stalks, wood chips, bagasse, coffee grounds, etc.) and nylon fibers.

[0041] Among them, the selected flow modifier can be one or a combination of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, 1,3-phenylbis(2-oxazoline), 1,4-phenylbis(2-oxazoline), bis(2-oxazoline), diglycidyl ether cyclic diepoxide, diimide diepoxide, phthaloyl biscaprolactam, etc.

[0042] Example 1

[0043] A halogen-free flame-retardant PC composite material with a high recycling ratio comprises the following components in parts by weight: 46.7 parts of PCR-PC1, 12 parts of PCR-PC2, 9 parts of a flame retardant, 0.8 parts of an anti-drip agent, 0.3 parts of an antioxidant, 30 parts of fiber, 0.4 parts of a flow modifier, and 0.8 parts of a colorant.

[0044] Specifically, the two selected PCR PCs are both bisphenol A linear polycarbonate, wherein 46.7 parts of PCR-PC1 are low-fluidity PCs, and 12 parts of PCR-PC2 are high-fluidity PCs.

[0045] 9 parts of the flame retardant are phosphate flame retardants.

[0046] 0.8 parts of the anti-dripping agent is a non-coated PTFE (pure powder type) type anti-dripping agent.

[0047] 0.3 parts of antioxidant is a phosphite antioxidant.

[0048] 30 parts of the fibers were glass fibers (GF).

[0049] 0.4 parts of the flow modifier is a cyanate ester flow modifier.

[0050] 0.8 parts of the colorant is carbon black powder.

[0051] When preparing the halogen-free flame-retardant PC composite material with a high recycling ratio, the components of corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded into granules. The processing machine is a twin-screw extruder, and the processing temperature is 280-290°C.

[0052] Example 2

[0053] A halogen-free flame-retardant PC composite material with a high recycling ratio comprises the following components in parts by weight: 46.4 parts of PCR-PC1, 12 parts of PCR-PC2, 9.3 parts of a flame retardant, 0.8 parts of an anti-drip agent, 0.3 parts of an antioxidant, 30 parts of glass fiber, 0.4 parts of a flow modifier, and 0.8 parts of a colorant.

[0054] Specifically, the two selected PCR PCs are both bisphenol A linear polycarbonate, wherein 46.4 parts of PCR-PC1 are low-fluidity PCs, and 12 parts of PCR-PC2 are high-fluidity PCs.

[0055] 9.3 parts of the flame retardant are phosphate flame retardants.

[0056] 0.8 parts of the anti-dripping agent is a non-coated PTFE (pure powder type) type anti-dripping agent.

[0057] 0.3 parts of antioxidant is a phosphite antioxidant.

[0058] 30 parts of the fibers were glass fibers (GF).

[0059] 0.4 parts of the flow modifier is a cyanate ester flow modifier.

[0060] 0.8 parts of the colorant is carbon black powder.

[0061] When preparing the halogen-free flame-retardant PC composite material with a high recycling ratio, the components of corresponding weight parts are weighed according to the above ratio, and the components are evenly mixed and then melt-extruded into granules. The processing machine is a twin-screw extruder, and the processing temperature is 280-290°C.

[0062] After the above embodiments were implemented, they were reproduced according to the same components. After the melt extrusion granulation of Embodiment 1 and Embodiment 2, the particles in each embodiment were injection molded into standard test specimens on an injection molding machine. The mechanical properties of the obtained materials were tested according to the standard. The test results are shown in Table 1:

[0063] Table 1 Test results

[0064]

[0065] From the test results of Example 1 and Example 2, it can be seen that the present invention achieves the preparation of a halogen-free flame-retardant PC composite material with a high recovery ratio by adding GF filler and utilizing processing aids.

[0066] The beneficial effects of the present invention are:

[0067] 1. The material of the present invention does not contain dangerous halogen compounds, so the risk of secondary pollution can be reduced when it is recycled and reused.

[0068] 2. The material of the present invention uses a high proportion of recycled materials (>50%), making it more environmentally friendly.

[0069] 3. The material of the present invention is mainly composed of PC, to which 10-50% GF filler is added. In addition to having certain mechanical properties and flame retardancy (1.0mm V-0), it also has a higher heat deformation temperature (>95°C), which can effectively increase its application range.

[0070] It should be pointed out that the present invention is not limited to the above-mentioned implementation modes, and any simple modifications, equivalent changes and modifications made to the above-mentioned embodiments by any technician familiar with the profession based on the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. A halogen-free flame-retardant PC composite material with a high recycling ratio, characterized in that: The composition comprises the following components in parts by weight: Polycarbonate (PCR PC), 40-84 parts by weight; Flame retardant, 5 to 15 parts by weight; Anti-dripping agent, 0.5 to 2 parts by mass; Antioxidant, 0.2-0.8 parts by weight; Fiber, 10-50 parts by weight; Flow improver, 0.3 to 0.8 parts by mass.

2. The halogen-free flame-retardant PC composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected polycarbonate can be a combination of two or more of bisphenol A linear polycarbonate, polyester polycarbonate, silicone copolymer polycarbonate, cyclohexane bisphenol A polycarbonate, and polycarbonate synthesized from bisphenol TMC. The melt mass flow rate of the polycarbonate is MI = (3-25) g / 10min (300°C / 1.2kg), and the impact strength is IS = (15-72) kJ / m 2 , the weight average molecular weight is between 10000 and 50000, and the molecular weight distribution is between 1 and 3.

3. The halogen-free flame-retardant PC composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected polycarbonate (PC RPC) recycled components are 90-100%, and the types of polycarbonate can be one or more combinations of recycled water bottle materials, water bottle material fragments, recycled CD materials, CD fragments, recycled headlamp shell materials, headlamp shell fragments, electronic product recycled materials and their fragments.

4. The halogen-free flame-retardant PC composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected flame retardant can be a compound of two types of phosphate flame retardants, sulfonate flame retardants, silicone flame retardants and their derivative flame retardants.

5. The halogen-free flame-retardant PC composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected anti-dripping agent is a fluorine-based PTFE material, including a core-shell coated PTFE material and a non-coated PTFE (pure powder type) material.

6. The halogen-free flame-retardant PC composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected antioxidant composition is one or a combination of hindered phenols, hindered amines and phosphites.

7. The halogen-free flame-retardant PC composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected fibers may be one or more composite fibers such as glass fiber (GF), carbon fiber, mineral fiber, natural plant fiber and nylon fiber.

8. The halogen-free flame-retardant PC composite material with a high recycling ratio as claimed in claim 1, characterized in that: The selected flow modifier can be one or a combination of 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, 1,3-phenylbis(2-oxazoline), 1,4-phenylbis(2-oxazoline), bis(2-oxazoline), diglycidyl ether cyclic diepoxide, diimide diepoxide, phthaloyl biscaprolactam, etc.

9. The halogen-free flame-retardant PC composite material with a high recycling ratio as claimed in claim 1, characterized in that: The processing machine selected is a twin-screw extruder, and the processing temperature is 280-290°C.

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