Polycarbonate composition as well as preparation method and application thereof

Abstract

The invention relates to a polycarbonate composition as well as a preparation method and application thereof. The polycarbonate composition comprises the following components in parts by weight: 55-75 parts of polycarbonate, 14-36 parts of ultra-high molecular weight polyethylene, 2-9 parts of diamond, 1-9 parts of a phosphate compound containing a benzene ring and 0.5-5 parts of a compatilizer. The polycarbonate composition has the advantages of low bending modulus, low hardness, low friction coefficient, high impact strength and good skin touch feeling, and is very suitable for preparing skin-friendly materials.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer material modification, and more particularly to a polycarbonate composition, a preparation method and application thereof. BACKGROUND

[0002] Skin-friendly materials are materials that give people a comfortable and friendly feeling when in contact with the human body. Common application fields include medical devices, children's toys, kitchen utensils, bedding, etc. Skin-friendly materials have certain elasticity, flexibility and friction, and can reduce the reaction when in contact with the skin.

[0003] Polycarbonate (PC) is a highly transparent amorphous thermoplastic and one of the five engineering plastics, and is widely used.

[0004] However, the bending modulus of polycarbonate is as high as 2200-2500 MPa (ISO 178 standard), and lacks elastic deformation ability when in contact, which is easy to form local pressure points on the skin. At the same time, the toughness of polycarbonate is low, the hardness is high, and the flexibility is insufficient, resulting in poor comfort of human skin touch. In addition, the surface of polycarbonate is smooth but highly polar, and the dry friction coefficient with the skin is 0.3-0.5 (ASTM D1894), which is much higher than that of skin-friendly materials such as silicone (0.1-0.2) or hydrogel (<0.1), which makes the dynamic friction of polycarbonate easily cause micro-damage to the epidermis. The above makes it difficult for polycarbonate to be used as a skin-friendly material.

[0005] The Chinese patent entitled Copolyester composition with low coefficient of friction incorporates additives such as waxes and organosiloxanes in the polymer composition to reduce the coefficient of friction, and uses impact modifiers to improve impact toughness, solving the problem of high friction coefficient of existing polymer compositions. However, the hardness and bending modulus of this patent are still high, and the skin touch comfort as a skin-friendly material is still poor. SUMMARY

[0006] The primary object of the present application is to overcome the above-mentioned problem that PC materials are difficult to be used as skin-friendly materials, and to provide a polycarbonate composition.

[0007] A further object of the present application is to provide a preparation method of the above-mentioned polycarbonate composition.

[0008] A further object of the present application is to provide the use of the above-mentioned polycarbonate composition in the preparation of skin-friendly parts.

[0009] A further object of the present application is to provide a skin-friendly part.

[0010] The above-mentioned objects of the present application are achieved by the following technical solutions: A polycarbonate composition is characterized in that it comprises the following components in parts by weight: polycarbonate 55-75 parts, ultra-high molecular weight polyethylene 14-36 parts, diamond 2-9 parts, benzene ring-containing phosphoric acid ester compound 1-9 parts, compatibility agent 0.5-5 parts.

[0011] The ultra-high molecular weight polyethylene can impart high impact strength and low friction coefficient to the polycarbonate composition; in addition, the addition of the ultra-high molecular weight polyethylene can also reduce the bending modulus and hardness of the polycarbonate composition. However, the friction coefficient of the polycarbonate composition still needs to be further reduced to meet the requirements of the skin-friendly material.

[0012] The inventors of the present application have found that the further simultaneous addition of diamond and benzene ring-containing phosphoric acid ester compound can significantly reduce the friction coefficient of the polycarbonate composition in a synergistic manner, by taking advantage of the low friction coefficient of diamond and the protective effect of the benzene ring-containing phosphoric acid ester compound on the ultra-high molecular weight polyethylene. At the same time, the benzene ring-containing phosphoric acid ester compound can also avoid the negative impact of the addition of diamond on the impact strength, and the impact strength of the polycarbonate composition is maintained.

[0013] That is, the polycarbonate composition of the present application has low bending modulus, hardness and friction coefficient, and has high impact strength, and is good for the skin touch, and is very suitable for preparing skin-friendly materials.

[0014] In the present application, the amount of polycarbonate can be specifically 55, 57, 59, 61, 63, 65, 68, 70, 72, 75 parts by weight or a range value formed by any two of the above values; the amount of ultra-high molecular weight polyethylene can be specifically 14, 16, 18, 20, 23, 25, 28, 30, 32, 34, 36 parts by weight or a range value formed by any two of the above values; the amount of diamond can be specifically 2, 4, 6, 8, 9 parts by weight or a range value formed by any two of the above values; the amount of benzene ring-containing phosphoric acid ester compound can be specifically 1, 2, 4, 6, 8, 9 parts by weight or a range value formed by any two of the above values; and the amount of compatibility agent can be specifically 0.5, 1, 2, 3, 4, 5 parts by weight or a range value formed by any two of the above values.

[0015] In the present application, polycarbonate is used as the main body resin, and the content of polycarbonate accounts for more than 40wt% of the polycarbonate composition.

[0016] Preferably, the polycarbonate has a melt index of 3-30 g / 10 min measured at 300℃ under 1.2 kg.

[0017] In the present application, the melt index of the polycarbonate can be measured according to the GB / T3682.1-2018 standard.

[0018] Preferably, the polycarbonate is at least one of bisphenol A polycarbonate or silicon copolymer polycarbonate.

[0019] More preferably, the polycarbonate includes at least 30wt% of silicon copolymer polycarbonate.

[0020] Further preferably, the polycarbonate includes 30-80% of silicon copolymer polycarbonate.

[0021] Further preferably, the polycarbonate includes 40-80% of silicon copolymer polycarbonate.

[0022] By regulating the content of silicon copolymer polycarbonate in the polycarbonate within this range, the obtained polycarbonate composition has lower flexural modulus and hardness, higher impact strength, and lower surface friction coefficient.

[0023] Preferably, the weight average molecular weight of the ultrahigh molecular weight polyethylene is 1200000-3500000; specifically, it can be 1200000, 1400000, 1500000, 1800000, 2000000, 2300000, 2500000, 2800000, 3000000, 3200000, 3500000, or a range value formed by any two of the above values.

[0024] In the present application, the weight average molecular weight of the ultrahigh molecular weight polyethylene can be measured according to ASTM D6474-2012, with the condition that the sample is dissolved using 1,2,4-trichlorobenzene at high temperature (>140℃), the molecular chain is separated by a chromatographic column, and the weight average molecular weight is calculated by combining a standard curve.

[0025] More preferably, the weight average molecular weight of the ultrahigh molecular weight polyethylene is 2300000-3000000.

[0026] By regulating the weight average molecular weight of the ultrahigh molecular weight polyethylene within this range, the obtained polycarbonate composition has lower hardness, higher impact strength, and lower surface friction coefficient.

[0027] Preferably, the diamond is a nanodiamond.

[0028] Preferably, the D50 particle size of the diamond is 10-150nm.

[0029] Preferably, the D50 particle size of the diamond is 25-40nm. By regulating within this range, the polycarbonate composition has lower flexural modulus, better impact strength, and lower friction coefficient.

[0030] In the present application, the D50 particle size of the diamond can be measured according to ISO 22412:2024. Preferably, the benzene ring-containing phosphonate compound is at least one of bisphenol A-bis(diphenyl phosphate) or tetraphenyl resorcinol diphosphate.

[0031] More preferably, the benzene ring-containing phosphonate compound is bisphenol A-bis(diphenyl phosphate).

[0032] When the benzene ring-containing phosphonate compound is bisphenol A-bis(diphenyl phosphate), the polycarbonate composition has a lower flexural modulus, a better impact strength, and a lower coefficient of friction.

[0033] Preferably, the compatibilizer is a maleic anhydride grafted elastomer.

[0034] More preferably, the maleic anhydride grafted elastomer is at least one of a maleic anhydride grafted SEBS or a maleic anhydride grafted POE.

[0035] Preferably, the polycarbonate composition further comprises other auxiliary agents in an amount of 0.1 to 3 parts.

[0036] More preferably, the other auxiliary agent is at least one of a lubricant or an antioxidant.

[0037] Further preferably, the amount of the lubricant is 0.1 to 1 part, including but not limited to oxidized polyethylene wax.

[0038] Further preferably, the amount of the antioxidant is 0.1 to 1 part, including but not limited to at least one of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid n-octadecyl ester, phosphite antioxidant, tris(2,4-di-tert-butylphenyl) phosphite, or pentaerythritol tetrakis(3-dodecylthiopropionate).

[0039] The preparation method of the polycarbonate composition comprises the following steps: mixing the components, melt extruding, and granulating to obtain the polycarbonate composition.

[0040] Preferably, the temperature of the melt extrusion is 140 to 270°C; the screw rotation speed of the extruder for the melt extrusion is 300 to 600 RPM, and the screw length-diameter ratio is 36 to 48:1.

[0041] The application of the polycarbonate composition in the preparation of a skin-friendly product is also within the protection scope of the present application.

[0042] A skin-friendly product is prepared from the polycarbonate composition.

[0043] Preferably, the skin-friendly product is a robot hand product, a robot head product, an earphone box, or an eye box.

[0044] Compared with the prior art, the polycarbonate composition of the present application has the advantages of: The polycarbonate composition of the present application has low bending modulus, hardness and friction coefficient, and high impact strength, and is good for skin touch, and is very suitable for preparing skin-friendly materials. DETAILED DESCRIPTION

[0045] In order to more clearly and completely describe the technical solutions of the present application, the present application is further described in detail below through specific examples, and it should be understood that the specific examples described herein are only used to explain the present application and are not used to limit the present application, and various changes can be made within the scope of the present application.

[0046] Some reagents selected for the embodiments and comparative examples of the present application are described as follows: Polycarbonate 1#: bisphenol A type polycarbonate, brand PC CH9115LT, manufacturer Cangzhou Dahua, MFR = 9 g / 10 min; Polycarbonate 2#: silicon copolymer polycarbonate, brand PC A1050, manufacturer Wanhua Chemical, MFR = 5 g / 10 min; Polycarbonate 3#: bisphenol A type polycarbonate, brand PC CH8225, manufacturer Cangzhou Dahua, MFR = 20 g / 10 min; The test conditions of MFR of the above polycarbonates are 300℃, 1.2 kg; Ultrahigh molecular weight polyethylene 1#: brand UH150P, manufacturer Celanese, weight average molecular weight about 1500000; Ultrahigh molecular weight polyethylene 2#: brand SEU-250E, manufacturer Yanshan Petrochemical, weight average molecular weight about 2500000; Ultrahigh molecular weight polyethylene 3#: brand 9300CG, manufacturer Yanshan Petrochemical, weight average molecular weight 3000000; Common polyethylene: brand DGDA6098, Sinopec, weight average molecular weight about 100000; Diamond 1#: DND-30, GRISH, D50 particle size 35 nm; Diamond 2#: DND-100, GRISH, D50 particle size 90 nm; Compatibilizer: FG1901, Kraton, SEBS grafted with maleic anhydride; Phenyl ring-containing phosphoric acid ester compound 1#: bisphenol A-bis (diphenyl phosphate), WSFR-BDP-N2, Zhejiang Wansheng; Phenyl ring-containing phosphoric acid ester compound 2#: tetraphenyl resorcinol diphosphate, STAB PFR, Aidi Ke; Triethyl phosphate: commercially available; Other additive 1#: antioxidant, Revonox 608, commercially available; Other additive 2#: lubricant, LICOWAX PED521, commercially available; Unless otherwise specified, each component (e.g. compatibilizer, other additive 1#, other additive 2#) used in each parallel example and comparative example is the same commercially available product.

[0047] The polycarbonate compositions provided by each example and comparative example of the present application were tested for performance according to the following test methods: (1) Flexural modulus test: ISO 178-2019; (2) Notched impact strength: ISO 180-2023, the notch type is A type notch; (3) Hardness Shore D: ISO 7619-1-2010; (4) Friction coefficient: according to ASTM D1894-2014: the polycarbonate composition is injection molded into a test plate of 63.5mm x 63.5mm, the test speed is controlled at 150±30mm / min, a standard slider (stainless steel material) with a mass of 200±5g is used, the friction coefficient is calculated by the ratio of friction force to vertical normal pressure; 5 test plates are tested for each example and comparative example, and then the average value is calculated.

[0048] The polycarbonate compositions of each example and each comparative example of the present application were prepared according to the following process: Each component was weighed according to the formula, mixed, and then added to a twin-screw extruder, melted and extruded, and granulated to obtain a polycarbonate composition. The temperature settings of each zone of the screw extruder were 140℃, 200℃, 240℃, 260℃, 250℃, 250℃, 250℃, 260℃, 250℃, and 270℃, respectively, the screw rotation speed was 500 revolutions per minute, and the screw length-diameter ratio was 40:1.

[0049] Examples 1~11 Examples 1~11 provide a series of polycarbonate compositions, the formulations of which are shown in Tables 1 and 2.

[0050] Table 1 Formulation of Examples 1~7 (parts by weight) .

[0052] Table 2 Formulation of Examples 8~11 (parts by weight) .

[0054] Comparative Examples 1~7 Comparative Examples 1 to 7 provide a series of polycarbonate compositions whose formulations are shown in Table 3.

[0055] Table 3 Formulations (parts by weight) of Comparative Examples 1 to 7 .

[0057] The properties of the polycarbonate compositions of each of the examples and comparative examples were measured according to the above-mentioned test methods, and the test results are shown in Table 4. Table 4 Property results of the polycarbonate compositions of each of the examples and comparative examples

[0058] From Table 4, it can be seen that: The polycarbonate compositions of Examples 1 to 11 all have a flexural modulus of 1752 MPa or less, an impact strength of 50 kJ / m 2 or more, a Shore hardness of 95 or less, and a surface friction coefficient of 0.18 or less.

[0059] Comparative Example 1 does not add ultra-high molecular weight polyethylene and instead uses an equal amount of ordinary polyethylene, and the polycarbonate composition has a flexural modulus that is too large, an impact strength that is too low, a hardness that is too high, and a friction coefficient that is too large.

[0060] Comparative Example 2 does not add ultra-high molecular weight polyethylene, and the polycarbonate composition has a flexural modulus that is large, an impact strength that is low, a hardness that is high, and a friction coefficient that is large.

[0061] Comparative Example 3 does not add diamond and does not add the benzene ring-containing phosphate ester compound, and the polycarbonate composition has a large surface friction coefficient.

[0062] Comparative Example 4 does not add diamond, and the polycarbonate composition still has a relatively large friction coefficient.

[0063] Comparative Example 5 does not add the benzene ring-containing phosphate ester compound, and the polycarbonate composition has a low impact strength and a large friction coefficient.

[0064] Comparative Example 6 does not add diamond and instead uses an equal amount of talc powder, and the polycarbonate composition has a low impact strength and a large friction coefficient.

[0065] Comparative Example 7 does not add the benzene ring-containing phosphate ester compound and instead uses an equal amount of triethyl phosphate, and the polycarbonate composition has a low impact strength and a large friction coefficient.

[0066] Obviously, the above embodiments of the present application are merely exemplary but not intended to limit the embodiments of the present application. Based on the above description, any other variations or changes can be made by those skilled in the art without departing from the spirit and principles of the present application. It is not necessary to list all the embodiments here. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present application shall fall within the scope of the claims of the present application.

Claims

1. A polycarbonate composition, characterized in that, The components include the following parts by weight: 55-75 parts polycarbonate 14-36 parts of ultra-high molecular weight polyethylene 2-9 parts diamond 1-9 parts of phosphate ester compounds containing benzene rings, Compatibilizer 0.5 to 5 parts.

2. The polycarbonate composition according to claim 1, characterized in that, The polycarbonate measured at 300℃ and 1.2kg had a melt index of 3~30g / 10min.

3. The polycarbonate composition according to claim 1, characterized in that, The polycarbonate comprises at least 30 wt% silicon-copolymerized polycarbonate.

4. The polycarbonate composition according to claim 1, characterized in that, The weight-average molecular weight of the ultra-high molecular weight polyethylene is 1,200,000 to 3,500,000.

5. The polycarbonate composition according to claim 1, characterized in that, The diamond is nanodiamond.

6. The polycarbonate composition according to claim 1, characterized in that, The benzene ring-containing phosphate compound is at least one of bisphenol A-bis(diphenyl phosphate) or tetraphenylresorcinol diphosphate.

7. The polycarbonate composition according to claim 1, characterized in that, The polycarbonate composition also includes 0.1 to 3 parts of other additives.

8. A method for preparing the polycarbonate composition according to any one of claims 1 to 7, characterized in that, The process includes the following steps: mixing the components, melt extruding, and granulating to obtain the polycarbonate composition.

9. The use of the polycarbonate composition according to any one of claims 1 to 7 in the preparation of skin-friendly parts.

10. A skin-friendly component, characterized in that, It is prepared from the polycarbonate composition according to any one of claims 1 to 7.

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