High-toughness polycarbonate modified material as well as preparation method and application thereof

Abstract

The invention discloses a high-toughness polycarbonate modified material as well as a preparation method and application thereof. The high-toughness polycarbonate modified material is prepared from the following components in parts by weight: 82 to 110 parts of polycarbonate, 4 to 7 parts of core-shell type impact modifier, 8 to 15 parts of filler, 1 to 3 parts of flame retardant, 0.15 to 1.5 parts of antioxidant and 0.1 to 0.5 part of lubricant, wherein the core-shell type impact modifier comprises the following components in parts by weight: 43-56 parts of an emulsifier, 90-113 parts of a polymeric monomer, 2.5-6 parts of a crosslinking monomer, 32-45 parts of a shell layer monomer and 0.1-1 part of an initiator, the polymeric monomer at least comprises acrylic acid and phenyl acrylate, and the mass ratio of the acrylic acid to the phenyl acrylate is 1: (0.8-1.2); the crosslinking monomer comprises diallyl phthalate and acrylic acid-2-phenyl propyl ester, and the mass ratio of the diallyl phthalate to the acrylic acid-2-phenyl propyl ester is 3: (0.5-1). The toughness of the carbonic ester can be improved through the position and interaction of benzene rings in a main chain and a branch chain in the molecular structure of the modifier.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a high-toughness polycarbonate modified material, a preparation method thereof, and an application thereof. Background Art

[0002] Polycarbonate is an amorphous thermoplastic and belongs to one of the five major engineering plastics. Polycarbonate has high rigidity, modulus, good high-temperature resistance performance and dimensional stability, and can also resist impact. It is used in many industries and products such as electronic and electrical, household appliances, office equipment, power tools, charging piles, etc. through various forms such as 3D printing and injection molding. With the rapid development of industry, traditional polycarbonate can no longer meet the needs of industrial manufacturing, and higher requirements are also put forward for the properties such as toughness and strength of polycarbonate.

[0003] For products produced from polycarbonate materials, the conventional polycarbonate materials and products without toughening modification have greater rigidity and brittleness, and fractures will occur during storage and use due to insufficient toughness, affecting the service life and quality. However, conventional toughening will affect the rigidity of the material. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-toughness polycarbonate modified material, a preparation method thereof, and an application thereof to solve the problems in the background art.

[0005] To achieve the above object, the technical solution adopted by the present invention is: a high-toughness polycarbonate modified material, comprising the following components in parts by weight: 82-110 parts of polycarbonate, 4-7 parts of core-shell impact modifier, 8-15 parts of filler, 1-3 parts of flame retardant, 0.15-1.5 parts of antioxidant, and 0.1-0.5 parts of lubricant;

[0006] Among them, the core-shell impact modifier comprises the following components in parts by weight: 43-56 parts of emulsifier, 90-113 parts of polymerization monomer, 2.5-6 parts of crosslinking monomer, 32-45 parts of shell monomer, and 0.1-1 part of initiator. The polymerization monomer includes at least acrylic acid and phenyl acrylate, and the mass ratio of the two is 1:(0.8-1.2). The crosslinking monomer includes diallyl phthalate and 2-phenylpropyl acrylate, and the mass ratio of the two is 3:(0.5-1).

[0007] As a further optimization, the shell monomer includes styrene and methyl methacrylate; the mass ratio of styrene to methyl methacrylate is 1:(1-1.2).

[0008] As a further optimization, the emulsifier is sodium dodecyl sulfate or sodium dodecylbenzene sulfonate; the initiator is potassium persulfate or azobisisobutyronitrile.

[0009] As a further optimization, the preparation method of the core-shell impact modifier comprises the following steps:

[0010] S101) Adding a polymerization monomer and a crosslinking monomer into an emulsifier solution to obtain a reaction solution;

[0011] S102) Adding an initiator into the reaction solution, reacting at 70-80 °C for 2-4 h to obtain a core layer solution;

[0012] S103) Dropwise adding a shell layer monomer and an initiator into the core layer solution, reacting at 70-90 °C for 3-5 h to obtain a core-shell polymerization solution;

[0013] S104) Washing and drying the polymerization solution to obtain the core-shell impact modifier.

[0014] As a further optimization, the filler is hollow glass microspheres, and the particle size of the hollow glass microspheres is 50-200 μm, preferably 80 μm.

[0015] As a further optimization, the flame retardant is one or more of sulfonate flame retardants, phosphate ester flame retardants and halogen-free flame retardants, and preferably a halogen-free flame retardant such as silicone polymer SFR-1000 is used.

[0016] As a further optimization, the antioxidant is antioxidant 1010 or antioxidant 168.

[0017] As a further optimization, the lubricant is pentaerythritol stearate.

[0018] The present invention also provides a preparation method of a high-toughness polycarbonate modified material, comprising the following steps:

[0019] S10) Preparing a core-shell impact modifier;

[0020] S20) Stirring and mixing polycarbonate, a core-shell impact modifier, a filler, a flame retardant, an antioxidant and a lubricant evenly according to mass parts to obtain a premix;

[0021] S30) Placing the premix in a twin-screw extruder, setting the zone temperature to 220-270 °C and the rotation speed to 300-500 rpm, extruding, cooling and pelletizing to obtain a high-toughness polycarbonate modified material.

[0022] The present invention also provides an application of the high-toughness polycarbonate modified material, using the high-toughness polycarbonate modified material for the outer shell of electronic appliances. For some conventional parts, they can be prepared by injection molding or the like, but for small-batch processed sample parts or those with a shell structure that is not easy to form, they can be prepared by 3D printing, such as processing polycarbonate into powder and then forming layer by layer through sintering.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] 1. By forming benzene ring structures in the main chain and the formed branched chains, the benzene ring in the main chain can endow the material with high strength, and the benzene ring in the branched chain can further form a cross-linked three-dimensional structure, which can improve the toughness characteristics of the material. Moreover, the interaction between the benzene ring in the main chain and the benzene ring in the branched chain can cause the benzene ring in the branched chain to be adsorbed near the benzene ring in the main chain, that is, the branched chain is bent or helical relative to the main chain, and this morphology can also avoid a loose three-dimensional structure, making the overall structure have higher toughness;

[0025] 2. 2-Phenylpropyl acrylate has a physical cross-linking effect. Its propyl branched chain increases the chain segment rigidity, can reduce the chain entanglement density, can form a locally ordered structure, enhance the toughness of the material, and can also assist chemical cross-linking. For example, when 2-phenylpropyl acrylate is added to the cross-linking monomer diallyl phthalate, the benzene ring in 2-phenylpropyl acrylate can adjust the distribution of the three-dimensional structure, can avoid brittleness caused by excessive cross-linking, and make the spatial distribution have better toughness. Specific embodiments

[0026] The following are specific embodiments of the present invention, which further describe the technical solutions of the present invention, but the present invention is not limited to these embodiments.

[0027] Example 1:

[0028] A high-toughness polycarbonate modified material comprises the following components by weight: 92 parts of polycarbonate, 7 parts of core-shell impact modifier, 14 parts of hollow glass microspheres, 2.2 parts of halogen-free flame retardant, 1.5 parts of antioxidant 1010, and 0.3 parts of pentaerythritol stearate;

[0029] Among them, the core-shell impact modifier comprises the following components by weight: 100 parts of water, 52 parts of sodium dodecyl sulfate, 95 parts of polymerization monomer, 6 parts of cross-linking monomer, 36 parts of shell monomer, and 0.5 parts of potassium persulfate. The polymerization monomer comprises 46 parts of acrylic acid and 49 parts of phenyl acrylate. The cross-linking monomer comprises 4.5 parts of diallyl phthalate and 1.5 parts of 2-phenylpropyl acrylate. The shell monomer comprises 18 parts of styrene and 18 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) adding the polymerization monomer and the cross-linking monomer into the sodium dodecyl sulfate solution to obtain a reaction solution; S102) adding potassium persulfate into the reaction solution and reacting at 70-80°C for 2-4 hours to obtain a core layer solution; S103) dropping the shell monomer and potassium persulfate into the core layer solution and reacting at 70-90°C for 3-5 hours to obtain a core-shell polymerization solution; S104) washing and drying the polymerization solution to obtain the core-shell impact modifier.

[0030] A preparation method of a high-toughness polycarbonate modified material, comprising the following steps:

[0031] S10) Prepare the core-shell impact modifier according to the above method;

[0032] S20) Stir and mix polycarbonate, core-shell impact modifier, hollow glass microspheres, halogen-free flame retardant, antioxidant 1010 and pentaerythritol stearate evenly by mass parts to obtain a premix;

[0033] S30) Place the premix in a twin-screw extruder, set the zone temperature to 250 - 270 °C, the rotation speed to 450 rpm, extrude, cool, and pelletize to obtain the high-toughness polycarbonate modified material.

[0034] Example 2:

[0035] A high-toughness polycarbonate modified material, by weight parts, comprises the following components: 96 parts of polycarbonate, 7 parts of core-shell impact modifier, 10 parts of hollow glass microspheres, 2.2 parts of halogen-free flame retardant, 1.5 parts of antioxidant 1010, 0.3 parts of pentaerythritol stearate;

[0036] Among them, the core-shell impact modifier, by weight parts, comprises the following components: 100 parts of water, 52 parts of sodium dodecyl sulfate, 95 parts of polymerization monomer, 6 parts of crosslinking monomer, 36 parts of shell monomer and 0.5 parts of potassium persulfate. The polymerization monomer includes 50 parts of acrylic acid and 45 parts of phenyl acrylate. The crosslinking monomer includes 5 parts of diallyl phthalate and 1 part of 2-phenylpropyl acrylate. The shell monomer includes 18 parts of styrene and 18 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) Add the polymerization monomer and the crosslinking monomer into the sodium dodecyl sulfate solution to obtain a reaction solution; S102) Add potassium persulfate into the reaction solution, react at 70 - 80 °C for 2 - 4 h to obtain a core layer solution; S103) Dropwise add the shell monomer and potassium persulfate into the core layer solution, react at 70 - 90 °C for 3 - 5 h to obtain a core-shell polymerization solution; S104) Wash and dry the polymerization solution to obtain the core-shell impact modifier.

[0037] A preparation method of a high-toughness polycarbonate modified material, comprising the following steps:

[0038] S10) Prepare the core-shell impact modifier according to the above method;

[0039] S20) Stir and mix polycarbonate, core-shell impact modifier, hollow glass microspheres, halogen-free flame retardant, antioxidant 1010 and pentaerythritol stearate evenly by mass parts to obtain a premix;

[0040] S30) Place the premix in a twin-screw extruder, set the zone temperature to 250 - 270 °C, the rotation speed to 450 rpm, extrude, cool, and pelletize to obtain a high-toughness polycarbonate modified material.

[0041] Example 3:

[0042] A high-toughness polycarbonate modified material, comprising the following components by weight: 92 parts of polycarbonate, 4 parts of core-shell impact modifier, 15 parts of hollow glass microspheres, 2.5 parts of halogen-free flame retardant, 1 part of antioxidant 168, and 0.5 part of pentaerythritol stearate;

[0043] Among them, the core-shell impact modifier comprises the following components by weight: 100 parts of water, 50 parts of sodium dodecyl sulfate, 100 parts of polymerization monomer, 6 parts of crosslinking monomer, 32 parts of shell monomer, and 0.5 part of potassium persulfate. The polymerization monomer includes 50 parts of acrylic acid and 50 parts of phenyl acrylate. The crosslinking monomer includes 4.7 parts of diallyl phthalate and 1.3 parts of 2-phenylpropyl acrylate. The shell monomer includes 16 parts of styrene and 16 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) Add the polymerization monomer and crosslinking monomer to the sodium dodecyl sulfate solution to obtain a reaction solution; S102) Add potassium persulfate to the reaction solution and react at 70 - 80 °C for 2 - 4 h to obtain a core layer solution; S103) Dropwise add the shell monomer and potassium persulfate to the core layer solution and react at 70 - 90 °C for 3 - 5 h to obtain a core-shell polymerization solution; S104) Wash and dry the polymerization solution to obtain the core-shell impact modifier.

[0044] A preparation method of a high-toughness polycarbonate modified material, comprising the following steps:

[0045] S10) Prepare the core-shell impact modifier according to the above method;

[0046] S20) Stir and mix evenly the polycarbonate, core-shell impact modifier, hollow glass microspheres, halogen-free flame retardant, antioxidant 168, and pentaerythritol stearate according to the mass parts to obtain a premix;

[0047] S30) Place the premix in a twin-screw extruder, set the zone temperature to 250 - 270 °C, the rotation speed to 450 rpm, extrude, cool, and pelletize to obtain a high-toughness polycarbonate modified material.

[0048] Example 4:

[0049] A high-toughness polycarbonate modified material, comprising the following components by weight: 92 parts of polycarbonate, 7 parts of core-shell impact modifier, 14 parts of hollow glass microspheres, 2 parts of halogen-free flame retardant, 1.5 parts of antioxidant 1010, and 0.5 part of pentaerythritol stearate;

[0050] Among them, the core-shell impact modifier comprises the following components by weight parts: 100 parts of water, 50 parts of sodium dodecylbenzenesulfonate, 100 parts of polymerization monomer, 3 parts of crosslinking monomer, 36 parts of shell monomer, and 0.5 part of potassium persulfate. The polymerization monomer includes 50 parts of acrylic acid and parts of phenyl acrylate. The crosslinking monomer includes 2.5 parts of diallyl phthalate and 0.5 part of 2-phenylpropyl acrylate. The shell monomer includes 18 parts of styrene and 18 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) adding the polymerization monomer and the crosslinking monomer into the sodium dodecylbenzenesulfonate solution to obtain a reaction solution; S102) adding potassium persulfate into the reaction solution, and reacting at 70-80 °C for 2-4 h to obtain a core layer solution; S103) dropping the shell monomer and potassium persulfate into the core layer solution, and reacting at 70-90 °C for 3-5 h to obtain a core-shell polymerization solution; S104) washing and drying the polymerization solution to obtain the core-shell impact modifier.

[0051] A preparation method of a high-toughness polycarbonate modified material comprises the following steps:

[0052] S10) Preparing the core-shell impact modifier according to the above method;

[0053] S20) Stirring and mixing polycarbonate, core-shell impact modifier, hollow glass microspheres, halogen-free flame retardant, antioxidant 1010, and pentaerythritol stearate evenly by mass parts to obtain a premix;

[0054] S30) Placing the premix in a twin-screw extruder, setting the zone temperature to 250-270 °C, the rotation speed to 450 rpm, extruding, cooling, and pelletizing to obtain a high-toughness polycarbonate modified material.

[0055] Example 5:

[0056] A high-toughness polycarbonate modified material comprises the following components by weight parts: 90 parts of polycarbonate, 7 parts of core-shell impact modifier, 15 parts of hollow glass microspheres, 1.5 parts of halogen-free flame retardant, 1.5 parts of antioxidant 168, and 0.5 part of pentaerythritol stearate;

[0057] Among them, the core-shell impact modifier comprises the following components by weight parts: 110 parts of water, 40 parts of sodium dodecylbenzenesulfonate, 90 parts of polymerization monomers, 6 parts of crosslinking monomers, 36 parts of shell monomers and 0.5 part of potassium persulfate. The polymerization monomers include 45 parts of acrylic acid and 45 parts of phenyl acrylate. The crosslinking monomers include 4.5 parts of diallyl phthalate and 1.5 parts of 2-phenylpropyl acrylate. The shell monomers include 36 parts of styrene and 36 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) adding the polymerization monomers and the crosslinking monomers into the sodium dodecylbenzenesulfonate solution to obtain a reaction solution; S102) adding potassium persulfate into the reaction solution, reacting at 70-80°C for 2-4 h to obtain a core layer solution; S103) dropping the shell monomers and potassium persulfate into the core layer solution, reacting at 70-90°C for 3-5 h to obtain a core-shell polymerization solution; S104) washing and drying the polymerization solution to obtain the core-shell impact modifier.

[0058] A preparation method of a high-toughness polycarbonate modified material comprises the following steps:

[0059] S10) Preparing the core-shell impact modifier according to the above method;

[0060] S20) Stirring and mixing polycarbonate, the core-shell impact modifier, hollow glass microspheres, a halogen-free flame retardant, antioxidant 168 and pentaerythritol stearate evenly according to mass parts to obtain a premix;

[0061] S30) Placing the premix in a twin-screw extruder, setting the zone temperature to 250-270°C, the rotation speed to 450 rpm, extruding, cooling and pelletizing to obtain the high-toughness polycarbonate modified material.

[0062] Comparative Example 1:

[0063] A high-toughness polycarbonate modified material comprises the following components by weight parts: 92 parts of polycarbonate, 7 parts of the core-shell impact modifier, 14 parts of hollow glass microspheres, 2.2 parts of a halogen-free flame retardant, 1.5 parts of antioxidant 1010 and 0.3 part of pentaerythritol stearate;

[0064] Among them, the core-shell impact modifier comprises the following components by weight: 100 parts of water, 52 parts of sodium dodecyl sulfate, 95 parts of polymerization monomer, 6 parts of crosslinking monomer, 36 parts of shell monomer and 0.5 part of potassium persulfate. The polymerization monomer comprises 46 parts of acrylic acid and 49 parts of butyl acrylate. The crosslinking monomer comprises 4.5 parts of diallyl phthalate and 1.5 parts of 2-phenylpropyl acrylate. The shell monomer comprises 18 parts of styrene and 18 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) adding the polymerization monomer and the crosslinking monomer into the sodium dodecyl sulfate solution to obtain a reaction solution; S102) adding potassium persulfate into the reaction solution and reacting at 70-80°C for 2-4 h to obtain a core layer solution; S103) dropping the shell monomer and potassium persulfate into the core layer solution and reacting at 70-90°C for 3-5 h to obtain a core-shell polymerization solution; S104) washing and drying the polymerization solution to obtain the core-shell impact modifier.

[0065] A preparation method of a high-toughness polycarbonate modified material comprises the following steps:

[0066] S10) preparing the core-shell impact modifier according to the above method;

[0067] S20) stirring and mixing polycarbonate, the core-shell impact modifier, hollow glass microspheres, a halogen-free flame retardant, antioxidant 168 and pentaerythritol stearate evenly by mass parts to obtain a premix;

[0068] S30) placing the premix in a twin-screw extruder, setting the zone temperature to 250-270°C, the rotation speed to 450 rpm, extruding, cooling and pelletizing to obtain the high-toughness polycarbonate modified material.

[0069] Comparative Example 2:

[0070] A high-toughness polycarbonate modified material comprises the following components by weight: 92 parts of polycarbonate, 7 parts of the core-shell impact modifier, 14 parts of hollow glass microspheres, 2.2 parts of halogen-free flame retardant, 1.5 parts of antioxidant 1010 and 0.3 part of pentaerythritol stearate;

[0071] Among them, the core-shell impact modifier comprises the following components by weight: 100 parts of water, 52 parts of sodium dodecyl sulfate, 95 parts of polymerization monomer, 6 parts of crosslinking monomer, 36 parts of shell monomer, and 0.5 part of potassium persulfate. The polymerization monomer includes 46 parts of acrylic acid and 49 parts of phenyl acrylate. The crosslinking monomer is ethylene glycol dimethacrylate. The shell monomer includes 18 parts of styrene and 18 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) adding the polymerization monomer and the crosslinking monomer into the sodium dodecyl sulfate solution to obtain a reaction solution; S102) adding potassium persulfate into the reaction solution, and reacting at 70-80°C for 2-4 h to obtain a core layer solution; S103) dropping the shell monomer and potassium persulfate into the core layer solution, and reacting at 70-90°C for 3-5 h to obtain a core-shell polymerization solution; S104) washing and drying the polymerization solution to obtain the core-shell impact modifier.

[0072] A preparation method of a high-toughness polycarbonate modified material comprises the following steps:

[0073] S10) Preparing the core-shell impact modifier according to the above method;

[0074] S20) Stirring and mixing polycarbonate, core-shell impact modifier, hollow glass microspheres, halogen-free flame retardant, antioxidant 1010, and pentaerythritol stearate evenly by mass to obtain a premix;

[0075] S30) Placing the premix in a twin-screw extruder, setting the zone temperature to 250-270°C, the rotation speed to 450 rpm, extruding, cooling, and pelletizing to obtain a high-toughness polycarbonate modified material.

[0076] Comparative Example 3:

[0077] A high-toughness polycarbonate modified material comprises the following components by weight: 92 parts of polycarbonate, 7 parts of core-shell impact modifier, 14 parts of hollow glass microspheres, 2.2 parts of halogen-free flame retardant, 1.5 parts of antioxidant 1010, and 0.3 part of pentaerythritol stearate;

[0078] Among them, the core-shell impact modifier comprises the following components by weight parts: 100 parts of water, 52 parts of sodium dodecyl sulfate, 95 parts of polymerizable monomer, 6 parts of crosslinking monomer, 36 parts of shell monomer and 0.5 part of potassium persulfate. The polymerizable monomer includes 46 parts of acrylic acid and 49 parts of phenyl acrylate. The crosslinking monomer is diallyl phthalate. The shell monomer includes 18 parts of styrene and 18 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) adding the polymerizable monomer and the crosslinking monomer into the sodium dodecyl sulfate solution to obtain a reaction solution; S102) adding potassium persulfate into the reaction solution, and reacting at 70-80°C for 2-4 h to obtain a core layer solution; S103) dropping the shell monomer and potassium persulfate into the core layer solution, and reacting at 70-90°C for 3-5 h to obtain a core-shell polymer solution; S104) washing and drying the polymer solution to obtain the core-shell impact modifier.

[0079] A preparation method of a high-toughness polycarbonate modified material comprises the following steps:

[0080] S10) preparing the core-shell impact modifier according to the above method;

[0081] S20) stirring and mixing polycarbonate, the core-shell impact modifier, hollow glass microspheres, a halogen-free flame retardant, antioxidant 1010 and pentaerythritol stearate evenly by mass parts to obtain a premix;

[0082] S30) placing the premix in a twin-screw extruder, setting the zone temperature to 250-270°C, the rotation speed to 450 rpm, extruding, cooling and pelletizing to obtain the high-toughness polycarbonate modified material.

[0083] Comparative Example 4:

[0084] A high-toughness polycarbonate modified material comprises the following components by weight parts: 92 parts of polycarbonate, 7 parts of the core-shell impact modifier, 14 parts of hollow glass microspheres, 2.2 parts of halogen-free flame retardant, 1.5 parts of antioxidant 1010 and 0.3 part of pentaerythritol stearate;

[0085] Among them, the core-shell impact modifier comprises the following components by weight: 100 parts of water, 52 parts of sodium dodecyl sulfate, 95 parts of polymerization monomer, 6 parts of crosslinking monomer, 36 parts of shell monomer, and 0.5 part of potassium persulfate. The polymerization monomer includes 46 parts of acrylic acid and 49 parts of phenyl acrylate. The crosslinking monomer includes 4.5 parts of diallyl phthalate and 1.5 parts of ethylene glycol dimethacrylate. The shell monomer includes 18 parts of styrene and 18 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) adding the polymerization monomer and the crosslinking monomer into the sodium dodecyl sulfate solution to obtain a reaction solution; S102) adding potassium persulfate into the reaction solution and reacting at 70-80°C for 2-4 h to obtain a core layer solution; S103) dropping the shell monomer and potassium persulfate into the core layer solution and reacting at 70-90°C for 3-5 h to obtain a core-shell polymerization solution; S104) washing and drying the polymerization solution to obtain the core-shell impact modifier.

[0086] A preparation method of a high-toughness polycarbonate modified material comprises the following steps:

[0087] S10) preparing the core-shell impact modifier according to the above method;

[0088] S20) stirring and mixing polycarbonate, the core-shell impact modifier, hollow glass microspheres, a halogen-free flame retardant, antioxidant 1010, and pentaerythritol stearate evenly by mass parts to obtain a premix;

[0089] S30) placing the premix in a twin-screw extruder, setting the zone temperature to 250-270°C, the rotation speed to 450 rpm, extruding, cooling, and pelletizing to obtain the high-toughness polycarbonate modified material.

[0090] Comparative Example 5:

[0091] A high-toughness polycarbonate modified material comprises the following components by weight: 105 parts of polycarbonate, 7 parts of the core-shell impact modifier, 2.2 parts of a halogen-free flame retardant, 1.5 parts of antioxidant 1010, and 0.3 part of pentaerythritol stearate;

[0092] Among them, the core-shell impact modifier comprises the following components in parts by weight: 100 parts of water, 52 parts of sodium dodecyl sulfate, 95 parts of polymerization monomer, 6 parts of crosslinking monomer, 36 parts of shell monomer, and 0.5 part of potassium persulfate. The polymerization monomer comprises 46 parts of acrylic acid and 49 parts of phenyl acrylate. The crosslinking monomer comprises 4.5 parts of diallyl phthalate and 1.5 parts of 2-phenylpropyl acrylate. The shell monomer comprises 18 parts of styrene and 18 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) adding the polymerization monomer and the crosslinking monomer into the sodium dodecyl sulfate solution to obtain a reaction solution; S102) adding potassium persulfate into the reaction solution, and reacting at 70-80°C for 2-4 h to obtain a core layer solution; S103) dropping the shell monomer and potassium persulfate into the core layer solution, and reacting at 70-90°C for 3-5 h to obtain a core-shell polymerization solution; S104) washing and drying the polymerization solution to obtain the core-shell impact modifier.

[0093] A preparation method of a high-toughness polycarbonate modified material comprises the following steps:

[0094] S10) preparing the core-shell impact modifier according to the above method;

[0095] S20) stirring and mixing polycarbonate, the core-shell impact modifier, hollow glass microspheres, a halogen-free flame retardant, antioxidant 1010, and pentaerythritol stearate evenly according to parts by mass to obtain a premix;

[0096] S30) placing the premix in a twin-screw extruder, setting the zone temperature to 250-270°C, the rotation speed to 450 rpm, extruding, cooling, and pelletizing to obtain the high-toughness polycarbonate modified material.

[0097] Comparative Example 6:

[0098] A high-toughness polycarbonate modified material comprises the following components in parts by weight: 92 parts of polycarbonate, 7 parts of the core-shell impact modifier, 14 parts of hollow glass microspheres, 2.2 parts of a halogen-free flame retardant, 1.5 parts of antioxidant 1010, and 0.3 part of pentaerythritol stearate;

[0099] Among them, the core-shell impact modifier comprises the following components by weight: 100 parts of water, 52 parts of sodium dodecyl sulfate, 95 parts of polymerization monomer, 6 parts of crosslinking monomer, 36 parts of shell monomer and 0.5 part of potassium persulfate. The polymerization monomer comprises 46 parts of acrylic acid and 49 parts of butyl acrylate. The crosslinking monomer comprises ethylene glycol dimethacrylate. The shell monomer comprises 18 parts of styrene and 18 parts of methyl methacrylate. The preparation method of the core-shell impact modifier comprises the following steps: S101) adding the polymerization monomer and the crosslinking monomer into the sodium dodecyl sulfate solution to obtain a reaction solution; S102) adding potassium persulfate into the reaction solution and reacting at 70-80°C for 2-4 h to obtain a core layer solution; S103) dropping the shell monomer and potassium persulfate into the core layer solution and reacting at 70-90°C for 3-5 h to obtain a core-shell polymerization solution; S104) washing and drying the polymerization solution to obtain the core-shell impact modifier.

[0100] A preparation method of a high-toughness polycarbonate modified material comprises the following steps:

[0101] S10) Preparing the core-shell impact modifier according to the above method;

[0102] S20) Stirring and mixing polycarbonate, the core-shell impact modifier, hollow glass microspheres, a halogen-free flame retardant, antioxidant 168 and pentaerythritol stearate evenly by mass parts to obtain a premix;

[0103] S30) Placing the premix in a twin-screw extruder, setting the zone temperature to 250-270°C, the rotation speed to 450 rpm, extruding, cooling and pelletizing to obtain the high-toughness polycarbonate modified material.

[0104] Application examples:

[0105] The granular high-toughness polycarbonate modified materials prepared in Examples 1 to 5 and Comparative Examples 1 to 6 were made into test specimens under the same conditions (injection molding or 3D printing) according to the ASTM standard for testing. The test conditions and test results are shown in the following table.

[0106]

[0107]

[0108] From the above experimental data, it can be seen that the tensile strengths of the materials prepared in Examples 1 to 5 and Comparative Examples 1 to 6 are similar, but the elongation at break and notched impact strength of the materials prepared in Examples 1 to 5 are significantly improved, and the elongation at break and impact toughness of the materials can be improved more excellently. Specifically, by comparing Comparative Examples 1 to 6 with Example 1, it can be known that: the material formed in Comparative Example 1 does not contain a benzene ring structure in the main chain of the core-shell impact modifier; the material formed in Comparative Example 2 does not contain a benzene ring structure in the side chain of the core-shell impact modifier; the material formed in Comparative Example 3 contains a benzene ring in the side chain of the core-shell impact modifier but does not contain an auxiliary cross-linking structure; the material formed in Comparative Example 4 contains a benzene ring and other chemical cross-linking structures in the side chain of the core-shell impact modifier; the material formed in Comparative Example 5 does not contain hollow glass microspheres; the material formed in Comparative Example 6 does not contain a benzene ring structure in both the main chain and the side chain of the core-shell impact modifier. Through the differences in the molecular chains and molecular structures of the above modifiers, it can be shown that on the premise that the benzene ring structures in the main chain and the side chain have good strength, the spatial three-dimensional structure can be changed by the interaction between the benzene ring structure in the main chain and the benzene ring structure in the side chain, and excellent elasticity and toughness can be obtained; moreover, on the premise that it is known that adding hollow glass microspheres can make the overall polycarbonate material lighter, from the data of Example 1 and Comparative Example 5, it can be seen that the spatial structures of the main chain (with a benzene ring) and the side chain (with a benzene ring) of the core-shell impact modifier can ensure that the strength of the polycarbonate is not affected or is less affected.

[0109] The specific embodiments described herein are merely illustrative of the spirit of the present invention. Those skilled in the art to which the present invention pertains can make various modifications or supplements to the described specific embodiments or use similar ways to substitute them, but will not deviate from the spirit of the present invention or exceed the scope defined by the appended claims.

Claims

1. A high-toughness polycarbonate modified material, characterized in that, It includes the following components by weight parts: 82 - 110 parts of polycarbonate, 4 - 7 parts of core - shell impact modifier, 8 - 15 parts of filler, 1 - 3 parts of flame retardant, 0.15 - 1.5 parts of antioxidant, and 0.1 - 0.5 parts of lubricant; Among them, the core - shell impact modifier includes the following components by weight parts: 43 - 56 parts of emulsifier, 90 - 113 parts of polymerization monomer, 2.5 - 6 parts of cross - linking monomer, 32 - 45 parts of shell monomer, and 0.1 - 1 part of initiator. The polymerization monomer includes at least acrylic acid and phenyl acrylate, and the mass ratio of the two is 1:(0.8 - 1.2). The cross - linking monomer includes diallyl phthalate and 2 - phenylpropyl acrylate, and the mass ratio of the two is 3:(0.5 - 1).

2. The high-toughness polycarbonate modified material according to claim 1, characterized in that, The shell monomer includes styrene and methyl methacrylate; the mass ratio of styrene to methyl methacrylate is 1:(1 - 1.2).

3. The high-toughness polycarbonate modified material according to claim 1, wherein The emulsifier is sodium dodecyl sulfate or sodium dodecyl benzene sulfonate; the initiator is potassium persulfate or azobisisobutyronitrile.

4. The high-toughness polycarbonate modified material according to claim 1, characterized in that, The preparation method of the core - shell impact modifier includes the following steps: S101) Add the polymerization monomer and cross - linking monomer into the emulsifier solution to obtain a reaction solution; S102) Add the initiator into the reaction solution and react at 70 - 80 °C for 2 - 4 h to obtain a core layer solution; S103) Dropwise add the shell monomer and initiator into the core layer solution and react at 70 - 90 °C for 3 - 5 h to obtain a core - shell polymerization solution; S104) Wash and dry the polymerization solution to obtain the core - shell impact modifier.

5. The high-toughness polycarbonate modified material according to claim 1, characterized in that The filler is hollow glass microspheres, and the particle size of the hollow glass microspheres is 50 - 200 μm.

6. The high-toughness polycarbonate modified material according to claim 1, wherein The flame retardant is one or more of sulfonate flame retardants, phosphate flame retardants, and halogen - free flame retardants.

7. The high-toughness polycarbonate modified material according to claim 1, wherein The antioxidant is antioxidant 1010 or antioxidant 168.

8. The high-toughness polycarbonate modified material according to claim 1, characterized in that The lubricant is pentaerythritol stearate.

9. A method for preparing a high-toughness polycarbonate modified material according to any one of claims 1 to 8, characterized in that, It includes the following steps: S10) Prepare the core - shell impact modifier; S20) Stir and mix polycarbonate, core - shell impact modifier, filler, flame retardant, antioxidant, and lubricant evenly by mass parts to obtain a premix; S30) Place the premix in a twin - screw extruder, set the zone temperature to 220 - 270 °C, set the rotation speed to 300 - 500 rpm, extrude, cool, and pelletize to obtain a high - toughness polycarbonate modified material.

10. Use of the high-toughness polycarbonate modified material according to any one of claims 1 to 8, characterized in that, Use the high - toughness polycarbonate modified material for the outer shell of electronic appliances.

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