CN114539759A - Spraying-free polycarbonate material and preparation method thereof - Google Patents

Abstract

The invention provides a spraying-free polycarbonate material and a preparation method thereof. The spraying-free polycarbonate material comprises the following components in parts by weight: 90-98 parts of polycarbonate resin, 1-5 parts of toughening agent, 0.05-1 part of flame retardant and 0.2-0.8 part of flow modifier. The preparation method comprises the following steps: (1) mixing the components of the spray-free polycarbonate material to obtain a mixture; (2) and (2) extruding and plasticizing the mixture obtained in the step (1) to obtain the spraying-free polycarbonate material. The spraying-free polycarbonate material provided by the invention has good fluidity, flame retardance and mechanical properties, and can solve the problems of weld marks and the like in the forming process of the polycarbonate material, so that a product has a good spraying-free appearance effect.

Description

Spraying-free polycarbonate material and preparation method thereof

Technical Field

The invention belongs to the technical field of polymer composite materials, and particularly relates to a spraying-free polycarbonate material and a preparation method thereof.

Background

Plastic products such as electronic products, toys, furniture and household appliances and the like usually meet different appearance requirements through spraying, but paint and a solvent are required for spraying, so that the environment is seriously polluted, and the health and safety of a human body are seriously influenced. With the enhancement of environmental protection consciousness of people, the spraying-free material is widely applied, and the spraying-free material aims at spraying, so that one-step injection molding of spraying is avoided. The spraying-free material is a material which can be directly injected, does not need spraying, does not need to modify a mould and does not have flow marks, and can form bright and colorful appearance effects by directly injecting or extruding different plastic parts. Therefore, the spray-free material is becoming a research focus of people.

CN113583425A discloses a high-gloss spray-free polycarbonate PC composition. The highlight spray-free polycarbonate PC composition comprises the following components: polycarbonate resin, ABS resin, white mineral oil, a silane coupling agent, modified polysiloxane, a flame retardant, a toughening agent, polymethyl methacrylate, an antioxidant and a lubricant, wherein the raw materials are prepared from the following components in parts: 100 parts of polycarbonate resin, 20-50 parts of ABS resin, 2-4 parts of white mineral oil, 0.02-0.08 part of silane coupling agent, 5-15 parts of modified polysiloxane, 15-25 parts of flame retardant, 5-10 parts of toughening agent, 7-15 parts of polymethyl methacrylate, 0.5-1 part of antioxidant and 0.1-0.5 part of lubricant. According to the technical scheme, the white mineral oil reacts with each component of the composition, so that the silicone oil can be better dispersed, and silicone oil molecules are anchored, so that the silicone oil molecules are not easy to migrate and separate out, and the long-acting stable scratch resistance is kept; meanwhile, the polyester modified polysiloxane and the polycarbonate have excellent compatibility, dispersibility and demolding property, so that the prepared polycarbonate composition has better surface glossiness.

CN111978491A discloses a hyperbranched polyester copolymer, a spray-free polycarbonate fiber-reinforced composite material and a preparation method thereof. The spraying-free polycarbonate fiber-reinforced composite material is prepared from the following raw materials: 57-80% of polycarbonate, 10-30% of glass fiber, 0.2-1% of hyperbranched polyester copolymer, 5-10% of toughening agent, 0.1-0.5% of antioxidant and 0.1-0.5% of anti-UV agent. According to the technical scheme, the spraying-free polycarbonate fiber-added composite material prepared by using the hyperbranched polyester copolymer has the advantages of low fiber floating on the surface, high gloss and scratch resistance.

CN110358277A discloses a spraying-free polycarbonate material with enhanced flexibility, a mobile phone shell and a preparation method thereof. The spraying-free polycarbonate material is composed of polycarbonate, an antioxidant, toner, metallic aluminum pigment and a toughening agent, and the mass percentages of the materials are respectively as follows: 90-94% of polycarbonate, 1.3-3% of a toughening agent, and an antioxidant: 0.5-1%, metallic aluminum pigment: 1.8-3% and toner: 1.5-3%, wherein the polycarbonate comprises aromatic polycarbonate and aliphatic polycarbonate, and the weight ratio of the aromatic polycarbonate to the aliphatic polycarbonate is 8-9: 0.88-1. According to the technical scheme, the flexibility of the material is enhanced by adding the aliphatic polycarbonate into the material, and the flowability of the spraying-free polycarbonate material is enhanced, so that a bonding line of a traditional spraying-free polycarbonate mobile phone shell is eliminated, and the quality appearance integrity of the mobile phone is ensured.

In practical application, for products with a slightly complex structure or products with larger sizes, the problem of poor flowability of a spraying product is avoided, and poor molding appearance such as welding marks, clamping lines and the like is easy to occur, so that the popularization and application of the products are influenced. At present, the main method for improving the fluidity of the polycarbonate composite material is to add a molecular chain scission agent or hyperbranched resin for improvement, but after the molecular chain scission agent is added, the mechanical property of the material can be greatly reduced, so that a product becomes brittle and cracks, and the hyperbranched resin can influence the flame retardance, the surface hardness and the heat resistance of the material, so that the product is easy to deform and the surface is easy to scratch.

Therefore, how to provide a spray-free polycarbonate material with better fluidity, mechanical properties and flame retardancy has become a technical problem to be solved at present.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a spraying-free polycarbonate material and a preparation method thereof. According to the invention, through the design of the components of the spraying-free polycarbonate material, the prepared polycarbonate material has better fluidity, the problems of weld marks and the like in the forming process of the polycarbonate material can be improved, and a better spraying-free appearance effect is obtained.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the invention provides a spraying-free polycarbonate material, which comprises the following components in parts by weight:

90-98 parts of polycarbonate resin, 1-5 parts of toughening agent, 0.05-1 part of flame retardant and 0.2-0.8 part of flow modifier.

According to the invention, through the design of the components of the spray-free polycarbonate material and the use of the flow modifier, the prepared spray-free polycarbonate material has good fluidity, flame retardance and mechanical properties, the problems of weld marks and the like in the molding process of the polycarbonate material can be improved, and a good spray-free appearance effect is obtained.

In the invention, the prepared spraying-free polycarbonate material has good fluidity and good mechanical property by controlling the content of the flow modifier within a specific range. If the content of the flow modifier is too low, the prepared spraying-free polycarbonate material has poor fluidity and easily generates the problems of weld marks and the like in the forming process; if the content of the flow modifier is too much, the prepared spraying polycarbonate material has poor mechanical properties and is easy to crack and other poor problems.

In the present invention, the polycarbonate resin may be present in an amount of 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, or the like by weight.

The weight portion of the toughening agent can be 1 portion, 1.5 portions, 2 portions, 2.5 portions, 3 portions, 3.5 portions, 4 portions, 4.5 portions or 5 portions, etc.

The weight parts of the flame retardant can be 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part and the like.

The flow modifier may be present in an amount of 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, or the like.

The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.

As a preferred technical scheme of the invention, the flow modifier is 1-octyl imidazole p-toluenesulfonate.

According to the invention, the micromolecule 1-octyl imidazole p-toluenesulfonate is selected as the flow modifier, so that the using amount of the flow modifier can be further reduced, and the prepared spraying-free polycarbonate material still has good fluidity under the condition of low using amount of the flow modifier.

In the invention, the 1-octyl imidazole p-toluenesulfonate can chemically react with the polycarbonate resin at normal temperature to enable the two to be tightly combined through bond energy, and the 1-octyl imidazole p-toluenesulfonate can freely move among polycarbonate molecular chains during high-temperature molding to reduce the winding force among the polycarbonate molecular chains, so that the flow property of the polycarbonate resin can be improved, further, appearance problems such as weld marks and the like in the molding process of the spray-free polycarbonate material are avoided, and a better appearance effect is obtained.

As a preferable embodiment of the present invention, the melt index of the polycarbonate resin is 15 to 30g/10min, and may be, for example, 15g/10min, 16g/10min, 17g/10min, 18g/10min, 19g/10min, 20g/10min, 21g/10min, 22g/10min, 23g/10min, 24g/10min, 25g/10min, 26g/10min, 27g/10min, 28g/10min, 29g/10min or 30g/10 min.

As a preferred embodiment of the present invention, the toughening agent is selected from a methyl methacrylate-butadiene-styrene copolymer and/or an organosilicon polymer-polymethyl methacrylate.

Preferably, the grain size of the toughening agent is 50-100 μm, for example, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm or 100 μm.

In a preferred embodiment of the present invention, the flame retardant is selected from any one or a combination of at least two of trapezoidal polysilsesquioxane sulfonate, potassium diphenylsulfone sulfonate, and potassium perfluorobutyl sulfonate.

In a preferred embodiment of the present invention, the spray-free polycarbonate material further comprises 0.1 to 1 part of an antioxidant, which may be, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, or 1 part.

Preferably, the antioxidant is selected from any one of antioxidant 1076 (beta-octadecyl propionate), antioxidant 2921 or antioxidant 923 or the combination of at least two of the antioxidants.

In a preferred embodiment of the present invention, the spray-free polycarbonate material further comprises 0.1 to 1 part of an anti-dripping agent, which may be, for example, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, or 1 part.

Preferably, the anti-drip agent comprises polytetrafluoroethylene resin.

Preferably, the weight average molecular weight of the polytetrafluoroethylene resin is 400 to 500 ten thousand, and may be, for example, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, or 500 ten thousand.

In a second aspect, the present invention provides a method for preparing a spray-free polycarbonate according to the first aspect, comprising the steps of:

(1) mixing the components of the spray-free polycarbonate material to obtain a mixture;

(2) and (2) extruding and plasticizing the mixture obtained in the step (1) to obtain the spraying-free polycarbonate material.

As a preferable technical scheme of the invention, the mixing time is 10-15 min, for example, 10min, 11min, 12min, 13min, 14min or 15 min.

Preferably, the method of mixing is stirring.

Preferably, the rotation speed of the stirring is 10-20 rpm, for example, 10rpm, 11rpm, 12rpm, 13rpm, 14rpm, 15rpm, 16rpm, 17rpm, 18rpm, 19rpm or 20rpm, etc.

Preferably, the extrusion plasticizing method is to use a twin-screw extruder for extrusion plasticizing.

Preferably, the extrusion temperature of the extrusion plasticizing is 230 to 270 ℃, and may be 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃, 265 ℃ or 270 ℃ or the like, for example.

Preferably, the extrusion plasticizing step further comprises a post-treatment step.

Preferably, the post-treatment method comprises water cooling by drawing bars, air cooling and pelletizing.

As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:

(1) stirring and mixing all components of the spray-free polycarbonate material for 10-15 min at 10-20 rpm to obtain a mixture;

(2) and (2) extruding and plasticizing the mixture obtained in the step (1) by using a double-screw extruder, and then carrying out bracing water cooling, air cooling and grain cutting to obtain the spraying-free polycarbonate material, wherein the extrusion temperature is 230-270 ℃.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, through the design of the components of the spray-free polycarbonate material, 1-octyl imidazole p-toluenesulfonate is further used as a flow modifier, and the content of the 1-octyl imidazole p-toluenesulfonate is controlled within a specific range, so that the prepared spray-free polycarbonate material has good fluidity, flame retardance and mechanical properties, the melt index of the spray-free polycarbonate material is 35-68 g/10min, the spray-free polycarbonate material can pass a flame retardance test, the tensile modulus of the spray-free polycarbonate material is 2270-2320 MPa, the yield stress of the spray-free polycarbonate material is 57-63 MPa, and the IZOD notch impact strength at 23 ℃ is 61-72 KJ/m²。

Detailed Description

For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Some of the component sources in the examples and comparative examples are as follows:

polycarbonate resin: kesichuang, PC 2400;

methyl methacrylate-butadiene-styrene copolymer: brillouin, japan, M-701;

ladder polysilsesquioxane sulfonate: bolt containing organosilicon flame retardant, FR-SI-9805;

polytetrafluoroethylene resin: U.S. Pat. No. 3M, TF-1645;

thermoplastic acrylonitrile-styrene polymer: langshen, Germany 552495.

Example 1

The embodiment provides a spraying-free polycarbonate material and a preparation method thereof, wherein the spraying-free polycarbonate material comprises the following components in parts by weight:

96 parts of polycarbonate resin, 3 parts of methyl methacrylate-butadiene-styrene copolymer, 0.3 part of trapezoidal polysilsesquioxane sulfonate, 0.2 part of 1-octyl imidazole p-toluenesulfonate, 10760.2 parts of antioxidant and 0.5 part of polytetrafluoroethylene resin.

The preparation method of the spray-free polycarbonate resin comprises the following steps:

(1) stirring and mixing all components of the spray-free polycarbonate material for 12min at 15rpm to obtain a mixture;

(2) and (2) extruding and plasticizing the mixture obtained in the step (1) by using a double-screw extruder, and then carrying out bracing water cooling, air cooling and grain cutting to obtain the spraying-free polycarbonate material, wherein the extrusion temperature is 250 ℃.

Examples 2 to 4

Examples 2 to 4 respectively provide a spray-free polycarbonate material and a preparation method thereof, which are different from example 1 only in that the parts by weight of the 1-octyl imidazole p-toluenesulfonate are 0.4 part, 0.6 part and 0.8 part respectively, and the other conditions are the same as example 1.

Example 5

This example provides a spray-free polycarbonate material and a method for preparing the same, which is different from example 2 only in that 1-octyl imidazole p-toluenesulfonate is replaced with a thermoplastic acrylonitrile-styrene polymer, and other conditions are the same as example 2.

In the embodiment, the prepared spraying-free polycarbonate material has poor fluidity by using a common high molecular flow modifier (thermoplastic acrylonitrile-styrene polymer) in the prior art, and the prepared spraying-free polycarbonate material has the problems of easy occurrence of weld marks and the like in the molding process, so that the appearance effect of the product is reduced.

Comparative example 1

The comparative example provides a spray-free polycarbonate material and a preparation method thereof, and is different from the polycarbonate material in the example 1 only in that the spray-free polycarbonate material does not contain 1-octyl imidazole p-toluenesulfonate and other conditions are the same as the example 1.

Comparative example 2

The comparative example provides a spraying-free polycarbonate material and a preparation method thereof, and is different from the preparation method of the example 2 only in that the weight part of the 1-octyl imidazole p-toluenesulfonate is 0.1 part, and other conditions are the same as the example 2.

In the comparative example, the content of the flow modifier (1-octyl imidazole p-toluenesulfonate) is too small, the flowability of the prepared spray-free polycarbonate material is poor, and the problem of weld marks is easy to occur in the molding process.

Comparative example 3

The comparative example provides a spraying-free polycarbonate material and a preparation method thereof, and is different from the preparation method of the example 2 only in that the weight part of the 1-octyl imidazole p-toluenesulfonate is 1 part, and other conditions are the same as the example 2.

In the comparative example, if the content of the flow modifier is too much, the prepared spraying-free polycarbonate material has poor mechanical property and is easy to crack and the like.

The properties of the spray-free polycarbonate materials provided in the above examples and comparative examples were tested as follows:

melt index: tested according to ASTM D1238 standard;

flame retardancy: testing according to the flame retardant material testing standard in UL-94-1985, and recording whether the flame retardant material can pass a 94V-0 level vertical burning test;

tensile modulus: testing according to ISO527 standard;

yield stress: testing according to ISO527 standard;

IZOD notched impact strength: tested according to ISO180-4A standard.

The results of the performance tests of the spray-free polycarbonate materials provided in the above examples and comparative examples are shown in table 1 below:

TABLE 1

As can be seen from the content in Table 1, the spraying-free polycarbonate material prepared by designing the components of the spraying-free polycarbonate material, further using 1-octyl imidazole p-toluenesulfonate as a flow modifier and controlling the content of the 1-octyl imidazole p-toluenesulfonate within a specific range has good fluidity, flame retardance and mechanical properties, has a melt index of 35-68 g/10min, passes a flame retardance test, and has a tensile modulus of 2270-2320 MPa, a yield stress of 57-63 MPa and an IZOD notched impact strength of 61-72 KJ/m at 23 DEG C²。

If the spray-free polycarbonate material does not contain a flow modifier (comparative example 1), the flow of the prepared spray-free polycarbonate material is inferior to that of example 2.

The applicant states that the present invention is illustrated by the detailed process flow of the present invention through the above examples, but the present invention is not limited to the above detailed process flow, that is, it does not mean that the present invention must rely on the above detailed process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The spraying-free polycarbonate material is characterized by comprising the following components in parts by weight:

90-98 parts of polycarbonate resin, 1-5 parts of toughening agent, 0.05-1 part of flame retardant and 0.2-0.8 part of flow modifier.

2. The spray-free polycarbonate material of claim 1, wherein the flow modifier is 1-octyl imidazole p-toluenesulfonate.

3. The spray-free polycarbonate material according to claim 1 or 2, wherein the polycarbonate resin has a melt index of 15 to 30g/10 min.

4. The spray-free polycarbonate material of any of claims 1-3, wherein the toughening agent is selected from a methyl methacrylate-butadiene-styrene copolymer and/or a silicone polymer-polymethyl methacrylate;

preferably, the grain size of the toughening agent is 50-100 μm.

5. The spray-free polycarbonate material of any one of claims 1-4, wherein the flame retardant is selected from any one of or a combination of at least two of trapezoidal polysilsesquioxane sulfonate, potassium diphenylsulfone sulfonate, or potassium perfluorobutyl sulfonate.

6. The spray-free polycarbonate material as claimed in any one of claims 1 to 5, further comprising 0.1 to 1 part of an antioxidant;

preferably, the antioxidant is selected from any one of antioxidant 1076, antioxidant 2921 or antioxidant 923 or a combination of at least two thereof.

7. The spray-free polycarbonate material as claimed in any one of claims 1 to 6, further comprising 0.1 to 1 part of anti-dripping agent;

preferably, the anti-drip agent comprises a polytetrafluoroethylene resin;

preferably, the weight average molecular weight of the polytetrafluoroethylene resin is 400 to 500 ten thousand.

8. A process for the preparation of a spray-free polycarbonate according to any of claims 1 to 7, comprising the steps of:

(1) mixing the components of the spray-free polycarbonate material to obtain a mixture;

(2) and (2) extruding and plasticizing the mixture obtained in the step (1) to obtain the spraying-free polycarbonate material.

9. The method according to claim 8, wherein the mixing time is 10 to 15 min;

preferably, the method of mixing is stirring;

preferably, the rotating speed of the stirring is 10-20 rpm;

preferably, the extrusion plasticizing method is to use a twin-screw extruder to perform extrusion plasticizing;

preferably, the extrusion temperature of the extrusion plasticizing is 230-270 ℃;

preferably, the extrusion plasticizing step further comprises a post-treatment step;

preferably, the post-treatment method comprises water cooling of the riblets, air cooling and pelletizing.

10. The method according to claim 8 or 9, comprising in particular the steps of:

(1) stirring and mixing all components of the spray-free polycarbonate material for 10-15 min at 10-20 rpm to obtain a mixture;

(2) and (2) extruding and plasticizing the mixture obtained in the step (1) by using a double-screw extruder, and then carrying out bracing water cooling, air cooling and grain cutting to obtain the spraying-free polycarbonate material, wherein the extrusion temperature is 230-270 ℃.