A high-rigidity flame-retardant PC material and preparation method thereof

Abstract

The invention discloses a high-rigidity flame-retardant PC material and a preparation method thereof, belonging to the field of polymer material modification; the high-rigidity flame-retardant PC material comprises: 99-84 parts of polycarbonate, 5-15 parts of octaethylene phenyl ether octa-claw structure hybrid siloxane polymer, 0.4 parts of an anti-dripping agent, 0.3 parts of a lubricant and 0.3 parts of an antioxidant; the octaethylene phenyl ether octa-claw structure hybrid siloxane polymer is prepared by a hydrogen-containing siloxane compound and a vinyl phenyl ether compound undergoing a silylation reaction under the action of a platinum catalyst; the PC material of the invention has a high modulus and impact strength as well as good flame retardancy, can improve the problem of deformation caused by insufficient rigidity and heat resistance when the flame-retardant PC is applied to a thin-walled housing of consumer electronics, so that the PC material is more widely used in the field of lightweight and thin consumer electronic products.

Description

Technical Field

[0001] The invention belongs to the field of polymer material modification, and in particular relates to a high-rigidity flame-retardant PC material and a preparation method thereof. Background Art

[0002] As consumers pursue aesthetics, electronic products tend to be more and more lightweight. Lightweight structures have higher requirements for product deformation resistance. When the product is subjected to force or heat, it is more likely to cause deformation and warping, thus affecting the normal use of the product. For the application of lightweight products, it is necessary to improve the rigidity of the material to cope with the deformation and warping caused by the lightweight structure. The traditional method to improve the rigidity of the material is to add some inorganic reinforcing fillers such as glass fiber and minerals, but these fillers will cause corresponding defects such as floating fibers, loss of gloss, and whitening on the surface of the material. Therefore, it is particularly important to develop a high-rigidity flame-retardant PC material that does not affect the appearance. Summary of the invention

[0003] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a high-rigidity flame-retardant PC material and a preparation method thereof, which solves the problems in the prior art.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A flame retardant PC material, comprising the following raw materials in parts by weight:

[0006]

[0007]

[0008] The octaethyl paraphenylene ether octa-claw structure hybrid siloxane polymer is prepared by a hydrogen-containing siloxane compound and a vinyl paraphenylene ether compound undergoing a hydrosilylation reaction under the action of a platinum catalyst.

[0009] Furthermore, the structural formula of the octaethylparaphenylene ether octa-claw structure hybrid siloxane polymer is as follows:

[0010]

[0011] Wherein, the R group is an ethane-p-phenylene ether group, and its structural formula is as follows:

[0012]

[0013] Furthermore, the PC melt mass flow rate is 10 g / 10 min at 300° C. and 1.2 kg.

[0014] Furthermore, the anti-dripping agent is coated polytetrafluoroethylene.

[0015] Furthermore, the lubricant is pentaerythritol stearate.

[0016] Furthermore, the antioxidant is a phosphite antioxidant.

[0017] Furthermore, the antioxidant is 168 antioxidant.

[0018] The above-mentioned method for preparing a flame retardant PC material comprises the following steps:

[0019] S1, mixing PC, octaethyl paraphenylene ether octa-claw structure hybrid siloxane polymer, anti-dripping agent, lubricant and antioxidant to obtain a mixed material;

[0020] S2, feeding the mixed material into a twin-screw extruder through a main feeding port, and after shearing, melt plasticization, extrusion granulation, and homogenization, the mixed material is obtained.

[0021] Furthermore, the barrel temperatures of zones 1 to 9 and the head of the twin-screw extruder are 200°C, 270°C, 270°C, 270°C, 270°C, 260°C, 260°C, 250°C, 230°C, and 250°C respectively; the main engine speed is 400r / min, the current is 33A, and the vacuum degree is -0.09MPa.

[0022] The above-mentioned flame-retardant PC material is used in the preparation of lightweight electronic product casings.

[0023] Beneficial effects of the present invention:

[0024] 1. The present invention provides a high-rigidity flame-retardant PC material, which is different from traditional glass fiber and mineral reinforced materials, but has the same rigidity modulus as traditional reinforced materials, and does not have the appearance defects of traditional reinforced materials, such as floating fibers, loss of gloss, whitening, etc. It can be widely used in thin-walled consumer electronic products to solve the warping deformation caused by external force and heat caused by thin-wall.

[0025] 2. Octa-phenylene ether octa-claw structure hybrid siloxane polymer is a polymer with a high content of benzene ring structure in the molecular chain repeating structural unit. The steric hindrance volume of the benzene ring is large, which can hinder the movement of the molecular chain segments and thus show rigidity. The high density of benzene ring structural units on its molecular chain makes it show ultra-high modulus and rigidity in the macro structure, so that the polymer has the effect of increasing rigidity. At the same time, the introduction of phenyl can improve the compatibility of octa-phenylene ether octa-claw structure hybrid siloxane polymer in PC, because phenyl as an inert end group can prevent Si-O-Si gelation and facilitate its uniform dispersion in the PC matrix, so that the modified PC resin obtains higher modulus and rigidity. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solution of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] A high-rigidity flame-retardant PC material, comprising the following raw materials in parts by weight:

[0028] PC 99-84 copies;

[0029]

[0030] The octaethyl paraphenylene ether octa-claw structure hybrid siloxane polymer is prepared by a hydrosilylation reaction of a hydrogen-containing siloxane compound and a vinyl paraphenylene ether compound under the action of a platinum catalyst;

[0031] The structural formula of octaethyl paraphenylene ether octa-claw structure hybrid siloxane polymer is as follows:

[0032]

[0033] Wherein, the R group is an ethane-p-phenylene ether group, and its structural formula is as follows:

[0034]

[0035] The PC melt mass flowability rate is 10 g / 10 min at 300° C. and 1.2 kg.

[0036] The anti-dripping agent is coated polytetrafluoroethylene.

[0037] The lubricant is PETS (pentaerythritol stearate).

[0038] The antioxidant is a phosphite antioxidant.

[0039] The method for preparing the above-mentioned high-rigidity flame-retardant PC material comprises the following steps:

[0040] S1, mixing PC, octaethyl paraphenylene ether octa-claw structure hybrid siloxane polymer, anti-dripping agent, lubricant and antioxidant in the above-mentioned parts by weight to obtain a mixed material;

[0041] S2, feeding the mixed material into a twin-screw extruder through a main feeding port, and after shearing, melt plasticization, extrusion granulation, and homogenization in the twin-screw extruder, the high-rigidity flame-retardant PC material is obtained;

[0042] Among them, the twin-screw extruder is a 35 machine, and the barrel temperatures of zones one to nine and the head are: 200℃, 270℃, 270℃, 270℃, 270℃, 260℃, 260℃, 250℃, 230℃, 250℃; the main engine speed is 400r / min, the current is 33A, and the vacuum degree is -0.09MPa.

[0043] The technical scheme of the present invention is described below by the following examples and comparative examples;

[0044] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0045] Polycarbonate (PC), brand 2100, manufacturer Wanhua;

[0046] Anti-drip agent, DB10, Shanghai Puxin Polymer Materials Co., Ltd.;

[0047] Lubricant, PETS-AP, manufactured by Italy Faji;

[0048] Antioxidant, 168 antioxidant, manufactured by Tianjin Lianlong.

[0049] Octaethylparaphenylene ether octa-claw structure hybrid siloxane polymer is homemade, and the specific preparation process is as follows:

[0050] Step 1, weighing octahydrogen cage-type polysilsesquioxane and vinyl paraphenylene ether in a molar ratio of 1:8, pouring them into a flask and magnetically stirring for 5 minutes to fully mix them, and sealing them with plastic wrap;

[0051] Step 2, weighing 1wt% of silicone oil platinum catalyst (based on vinyl paraphenylene ether), adding it to the mixed solution of step 1, and continuing to stir for 3min, placing the stirred mixed solution in a vacuum drying oven for vacuum defoaming, and after the bubbles are eliminated, sealing it again with plastic wrap to prevent impurities from mixing;

[0052] Step 3, placing the reaction mixture of step 2 in a 25°C oven for pre-reaction for 12 hours, at which time the reaction system is a viscous liquid. This step is to avoid excessively intense early reaction and explosion of the reaction system;

[0053] Step 4, then raise the oven temperature in step 3 to 60°C, and continue heating and curing for 6 hours. At this time, the reaction system is a soft elastic body. This step is the initial curing stage;

[0054] Step 5, finally raising the oven temperature in step 4 to 100°C, and continuing the heating curing reaction for 1 hour to allow the reaction to be fully completed. At this time, the reaction system is in the form of a hard solid block, which is an octaethyl paraphenylene ether octa-claw structure hybrid siloxane polymer. This step is the complete curing stage;

[0055] Step 6, crushing and grinding the solid block obtained in step 5 by a high-speed crusher to obtain the final octaethyl paraphenylene ether octa-claw structure hybrid siloxane polymer powder.

[0056] It is to be understood that the above raw materials and reagents are only examples of some specific embodiments of the present invention, so that the technical solution of the present invention is clearer, and it does not mean that the present invention can only use the above reagents, and the specific scope in the claims shall prevail. In addition, the "parts" described in the examples and comparative examples, unless otherwise specified, refer to parts by mass.

[0057] Example 1

[0058] 99 parts of polycarbonate, 5 parts of octaethylparaphenylene ether octa-claw structure hybrid siloxane polymer, 0.4 parts of anti-dripping agent, 0.3 parts of lubricant and 0.3 parts of antioxidant are mixed evenly, and then fed into a twin-screw extruder through a main feeding port. After shearing, melt plasticization and extrusion granulation in the twin-screw extruder, the mixture is homogenized to obtain the high-rigidity flame-retardant PC material.

[0059] Among them, the twin-screw extruder is a 35 machine, and the barrel temperatures of zones 1 to 9 and the head are: 200℃, 270℃, 270℃, 270℃, 270℃, 260℃, 260℃, 250℃, 230℃, 250℃; the main engine speed is 400r / min, the current is 33A, and the vacuum degree is -0.09MPa.

[0060] Example 2

[0061] 89 parts of polycarbonate, 10 parts of octaethylparaphenylene ether octa-claw structure hybrid siloxane polymer, 0.4 parts of anti-dripping agent, 0.3 parts of lubricant and 0.3 parts of antioxidant were mixed evenly, and then fed into a twin-screw extruder through a main feeding port. After shearing, melt plasticization and extrusion granulation in the twin-screw extruder, the mixture was homogenized to obtain the high-rigidity flame-retardant PC material.

[0062] Among them, the twin-screw extruder is a 35 machine, and the barrel temperatures of zones 1 to 9 and the head are: 200℃, 270℃, 270℃, 270℃, 270℃, 260℃, 260℃, 250℃, 230℃, 250℃; the main engine speed is 400r / min, the current is 33A, and the vacuum degree is -0.09MPa.

[0063] Example 3

[0064] 84 parts of polycarbonate, 15 parts of octaethylparaphenylene ether octa-claw structure hybrid siloxane polymer, 0.4 parts of anti-dripping agent, 0.3 parts of lubricant and 0.3 parts of antioxidant were mixed evenly, and then fed into a twin-screw extruder through a main feeding port. After shearing, melt plasticization and extrusion granulation in the twin-screw extruder, the mixture was homogenized to obtain the high-rigidity flame-retardant PC material.

[0065] Among them, the twin-screw extruder is a 35 machine, and the barrel temperatures of zones 1 to 9 and the head are: 200℃, 270℃, 270℃, 270℃, 270℃, 260℃, 260℃, 250℃, 230℃, 250℃; the main engine speed is 400r / min, the current is 33A, and the vacuum degree is -0.09MPa.

[0066] Comparative Example 1

[0067] 99 parts of the polycarbonate, 0 parts of octaethylparaphenylene ether octa-claw structure hybrid siloxane polymer, 0.4 parts of anti-dripping agent, 0.3 parts of lubricant and 0.3 parts of antioxidant were mixed uniformly according to weight parts, and then fed into a twin-screw extruder through a main feeding port. After shearing, melt plasticization and extrusion granulation in the twin-screw extruder, the mixture was homogenized to obtain a PC material.

[0068] Among them, the twin-screw extruder is a 35 machine, and the barrel temperatures of zones 1 to 9 and the head are: 200℃, 270℃, 270℃, 270℃, 270℃, 260℃, 260℃, 250℃, 230℃, 250℃; the main engine speed is 400r / min, the current is 33A, and the vacuum degree is -0.09MPa.

[0069] The specific formula of a PC material prepared in Examples 1-3 and Comparative Example 1 is shown in Table 1 below:

[0070] Table 1 Formulations of Examples 1-3 and Comparative Example 1

[0071]

[0072]

[0073] Experimental testing

[0074] The PC materials prepared in Examples 1-3 and Comparative Example 1 were subjected to performance tests, and the test results are shown in Table 2 below:

[0075] Table 2 Performance test results of PC materials prepared in Examples 1-3 and Comparative Example 1

[0076]

[0077] It can be seen from Table 2 that the modulus and flame retardancy of Comparative Example 1 are the worst, while Example 2 has higher tensile modulus, flexural modulus, thin-wall V-0 flame retardancy and better gloss. Therefore, the scheme of Example 2 is more suitable for preparing a high-rigidity flame-retardant PC material.

[0078] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0079] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A flame retardant PC material, characterized in that: Including the following raw materials by weight: The octaethyl paraphenylene ether octa-claw structure hybrid siloxane polymer is prepared by a hydrogen-containing siloxane compound and a vinyl paraphenylene ether compound undergoing a hydrosilylation reaction under the action of a platinum catalyst.

2. A flame retardant PC material according to claim 1, characterized in that: The structural formula of the octaethylparaphenylene ether octa-claw structure hybrid siloxane polymer is as follows: Wherein, the R group is an ethane-p-phenylene ether group, and its structural formula is as follows:

3. The flame retardant PC material according to claim 1, characterized in that: The PC melt mass flowability rate is 10 g / 10 min at 300° C. and 1.2 kg.

4. The flame retardant PC material according to claim 1, characterized in that: The anti-dripping agent is coated polytetrafluoroethylene.

5. The flame retardant PC material according to claim 1, characterized in that: The lubricant is pentaerythritol stearate.

6. The flame retardant PC material according to claim 1, characterized in that: The antioxidant is a phosphite antioxidant.

7. The flame retardant PC material according to claim 6, characterized in that: The antioxidant is 168 antioxidant.

8. A method for preparing a flame retardant PC material according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1, mixing PC, octaethyl paraphenylene ether octa-claw structure hybrid siloxane polymer, anti-dripping agent, lubricant and antioxidant to obtain a mixed material; S2, feeding the mixed material into a twin-screw extruder through a main feeding port, and after shearing, melt plasticization, extrusion granulation, and homogenization, the mixed material is obtained.

9. The method for preparing a flame retardant PC material according to claim 8, characterized in that: The barrel temperatures of zones 1 to 9 and the head of the twin-screw extruder are 200°C, 270°C, 270°C, 270°C, 270°C, 260°C, 260°C, 250°C, 230°C, and 250°C respectively; the main engine speed is 400r / min, the current is 33A, and the vacuum degree is -0.09MPa.

10. Use of the flame-retardant PC material according to any one of claims 1 to 7 in preparing a lightweight electronic product casing.

Images