A polycarbonate composite material and a method for producing the same

Abstract

The application discloses a polycarbonate composite material and a preparation method thereof. The polycarbonate composite material is prepared from the following components by mass percentage: polycarbonate 25-85%; surface epoxy modified glass beads 5-45%; toughening agent 0-15%; siloxane copolymer PC 10-45%; and antioxidant 0-0.4%. In the application, the surface epoxy modified glass beads have higher interfacial strength with the polycarbonate matrix, so that the polycarbonate composite material has higher tensile strength and impact strength, and better wear resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to a polycarbonate composite material, in particular to a polycarbonate composite material and a preparation method thereof. BACKGROUND

[0002] Polycarbonate (PC for short) is a high molecular polymer containing carbonate groups in the molecular chain. According to the structure of the ester group, it can be divided into aliphatic, aromatic, aliphatic-aromatic and other types. Polycarbonate is a strong and tough non-crystalline thermoplastic resin, which has excellent mechanical properties, heat resistance, optical and insulating properties, and is widely used in aerospace, automotive, information storage and other fields.

[0003] However, due to the high rigidity and large steric hindrance of the PC molecular chain, its main performance defects are not high enough in hydrolysis stability, sensitive to notches, poor in resistance to organic chemicals, scratch resistance and wear resistance, low in tensile strength and easy to crack, which to some extent limits the application.

[0004] In the published patent application CN1699473A, PC composite material is modified by adding hollow glass beads (GB), solid glass beads, silica (SiO2) or calcium carbonate (CaCO3) and other particulate fillers, but due to physical mixing, the improvement of the mechanical properties of the material is not obvious.

[0005] In the published patent application CN107227011A, hollow glass beads coated with conductive particles are added to modify the PC material of carbon nanotubes, but only the electrical conductivity of the PC composite material can be improved. SUMMARY

[0006] The purpose of the present application is to provide a polycarbonate composite material and a preparation method thereof. By adding surface epoxy modified glass beads, the tensile strength, impact strength, wear resistance and other mechanical properties of the polycarbonate composite material can be significantly improved.

[0007] To achieve the above purpose, the technical solution adopted by the present application is as follows:

[0008] A polycarbonate composite material, comprising components made of the following mass percentages:

[0009]

[0010] In a preferred embodiment of the present application, the surface epoxy modified glass beads are solid glass beads with a true density of 2.3-2.7 g / cm 3 , and a particle size of 5-180 μm.

[0011] The toughening agent is selected from one or more of POE, POE-g-GMA, POE-g-MAH, EVA, ACR, EVA-g-GMA grafting polymer, SBS-g-GMA grafting polymer, MBS, SBS, EPR, EPDM, silicon-based toughening agent, EMA; preferably, the toughening agent is one or more of MBS, silicon-based toughening agent, EMA; preferably, the MBS toughening agent, the typical model is the commercially available product M732, M722 (Zhongyuan Chemical); the silicon-based toughening agent, the typical model is the commercially available product S-2001, S-2030 (Mitsubishi Rayon); the EMA toughening agent, the typical model is the commercially available product 1125AC, 1180AC, 1330AC (DuPont).

[0012] The siloxane copolymer PC is a copolymer of bisphenol A and polydimethylsiloxane, the weight average molecular weight of the copolymer is 18000-26000 g / mol, and the polydimethylsiloxane content is 1-60%, preferably 5-20%;

[0013] Preferably, the weight average molecular weight of the polycarbonate is 22000-24000 g / mol.

[0014] The antioxidant is selected from phosphite and / or hindered phenolic antioxidant; preferably, the antioxidant is one or more of antioxidants 168, 626, B900, S-9228, 686, 1076, 1010.

[0015] A method for preparing a polycarbonate composite material, comprising the following steps:

[0016] The polycarbonate, surface epoxy modified glass beads, toughening agent, siloxane copolymer PC, antioxidant are premixed and then extruded and granulated by a twin-screw extruder.

[0017] Preferably, the extrusion temperature of the twin-screw extruder is divided into eleven zones, which are 250-260℃, 270-280℃, 280-285℃, 280-285℃, 280-285℃, 280-285℃, 280-285℃, 280-285℃, 270-280℃, 250-260℃, 250-260℃, respectively.

[0018] The preparation method of the surface epoxy modified glass beads, comprising the following steps:

[0019] A. The glass beads are added to a strong acid solution for surface roughening and hydroxylation;

[0020] B. The surface hydroxylated glass beads prepared in step A are added to an alkaline solution of glutaraldehyde for surface aldehyde group modification:

[0021] C. Preparation of DMSO solution of sulfur ylide;

[0022] D. Adding the surface aldehyde group modified glass beads prepared in step B to the solution prepared in step C to obtain surface epoxy modified glass beads.

[0023] The specific process of step A is as follows:

[0024] The glass beads are first added to dilute sulfuric acid, and the stirring is continued for 0.5-3 h to remove the surface impurities, and the glass beads are filtered out. Then the glass beads are added to a hydrofluoric acid solution, and after stirring at room temperature for 1-8 h, the glass beads are filtered out. The glass beads are washed with a 0.05-2% sodium carbonate aqueous solution, and then washed with deionized water until the pH value of the washing liquid is in the range of 6-8, and then dried to obtain the surface roughened and hydroxylated glass beads.

[0025] Preferably, the mass concentration of the dilute sulfuric acid is 0.5-3%, and the mass concentration of the hydrofluoric acid solution is 0.5-5%, preferably 1-2%. Preferably, the drying temperature is 70-90°C, the drying time is 3-24 h, and the drying method is vacuum drying.

[0026] The specific process of step B is as follows:

[0027] The surface hydroxylated glass beads prepared in step A are added to a 1-30%, preferably 2-5%, glutaraldehyde alkaline solution, and the mixture is heated to 50-70°C and stirred, and then filtered out and dried in air for 3-6 days to obtain the surface aldehyde group modified glass beads. The reaction process of step B can be represented by the following reaction formula:

[0028]

[0029] Preferably, the drying temperature is 80-120°C, and the drying time is 3-24 h. The glutaraldehyde alkaline solution is a sodium hydroxide solution, a potassium hydroxide solution, a pyridine-ethanol solution, or a pyrrole-ethanol solution of glutaraldehyde. In the glutaraldehyde alkaline solution, the mass fraction of sodium hydroxide is 0.5-20%, preferably 0.5-2%; or, the mass fraction of potassium hydroxide is 0.5-20%, preferably 0.5-2%; or, the mass fraction of pyridine is 1-30%, preferably 2-5%; or, the mass fraction of pyrrole is 1-30%, preferably 2-5%. The mass ratio of the amount of surface hydroxylated glass beads added in step B to the glutaraldehyde alkaline solution is 1:2-1:30, preferably 1:8-1:12.

[0030] The specific process of step C is as follows:

[0031] Dimethyl sulfide and methyl iodide with a molar ratio of 1:(0.8-1.3) are added to a DMSO (dimethyl sulfoxide) solution of 0.5-3% sodium hydroxide or potassium hydroxide, and the reaction is stirred at 0-10℃ for 1-10h, followed by the addition of sodium amide in multiple portions, and the stirring is continued for 0.5-2h to obtain a DMSO solution of sulfur ylide; the amount of the DMSO solution of sodium hydroxide or potassium hydroxide is 10-60 times the total mass of dimethyl sulfide and methyl iodide, and the amount of sodium amide is (1-1.5):1 in terms of the molar ratio of sodium amide to dimethyl sulfide.

[0032] Step C mainly occurs the following chemical reaction:

[0033]

[0034] The specific process of step D is as follows:

[0035] The surface aldehyde group modified glass beads prepared in step B are added to a sufficient amount of the sulfur ylide solution prepared in step C, and the stirring is continued at room temperature for 1-10h, then the product is taken out and dried in air for 3-6 days, and the reaction obtains the epoxy modified glass beads; step D mainly occurs the following chemical reaction:

[0036]

[0037] The beneficial effects of the present application relative to the prior art are as follows:

[0038] The polycarbonate composite material prepared by the prior art usually uses a silane coupling agent as a surface treatment agent for modified glass beads, but the glass beads treated by this method have a low grafting rate when applied to polycarbonate materials, and the prepared composite material has insufficient mechanical properties, especially low impact performance, losing the advantages of polycarbonate materials. The present application modifies the surface of glass beads with epoxy, which can crosslink with polycarbonate, and is combined with polycarbonate composite materials at a higher grafting rate, and the interfacial strength is significantly enhanced, thereby improving the tensile strength, impact strength, wear resistance and other mechanical properties of the polycarbonate composite material, and having a wider application space. DETAILED DESCRIPTION

[0039] The present application is further described below by specific examples, and the examples described in the present application are only used to illustrate the present application, and do not limit the scope of the present application.

[0040] The DMSO solution of sulfur ylide prepared by the following process is used in all embodiments of the present application:

[0041] Into 4 L of 1% potassium hydroxide DMSO solution, 62 g of dimethyl sulfide and 142 g of iodomethane were added, and the reaction was stirred at 0°C for 2 hours, followed by the addition of 39 g of sodium amide in several portions, and the stirring was continued for 1 hour to obtain a DMSO solution of sulfur ylide.

[0042] [Preparation Example 1] Preparation of surface epoxy-modified glass beads A

[0043] Into 5 L of 1% dilute sulfuric acid, 400 g of solid glass beads (Sovitec, 050-20-215) were added, and the stirring was continued for 1 hour to remove the surface impurities of the solid glass beads, and after filtration, the solid glass beads were added to 2 L of 0.5% hydrofluoric acid solution, and the mixture was stirred and heated to 60°C, and after standing for 2 hours, the solid glass beads were filtered out. The solid glass beads were washed with 1% sodium carbonate aqueous solution and then washed with deionized water for 5 times until the pH value of the washing solution was in the range of 6 to 8, and then the obtained solid glass beads were vacuum dried at 70°C for 24 hours, and then added to 4800 g of glutaraldehyde pyrrole-ethanol (mass ratio of pyrrole:ethanol = 2:98) solution (glutaraldehyde mass fraction 1%), and the reaction was stirred at room temperature for 3 hours, and then taken out and allowed to stand in air for 3 days, and then dried in an oven at 120°C for 24 hours to obtain solid glass beads with surface aldehyde groups.

[0044] Into 4 L of 1% potassium hydroxide DMSO solution, 62 g of dimethyl sulfide and 142 g of iodomethane were added, and the reaction was stirred at 0°C for 2 hours, followed by the addition of 39 g of sodium amide in several portions, and the stirring was continued for 1 hour to obtain a DMSO solution of sulfur ylide.

[0045] [Preparation Example 2] Preparation of surface epoxy-modified glass beads B

[0046] Into 5 L of 1% dilute sulfuric acid, 400 g of solid glass beads (Sovitec, 050-20-215) were added, and the stirring was continued for 1 hour to remove the surface impurities of the solid glass beads, and after filtration, the solid glass beads were added to 2 L of 0.5% hydrofluoric acid solution, and the mixture was stirred and heated to 60°C, and after standing for 2 hours, the solid glass beads were filtered out. The solid glass beads were washed with 1% sodium carbonate aqueous solution and then washed with deionized water for 5 times until the pH value of the washing solution was in the range of 6 to 8, and then the obtained solid glass beads were vacuum dried at 70°C for 24 hours, and then added to 4800 g of glutaraldehyde pyrrole-ethanol (mass ratio of pyrrole:ethanol = 2:98) solution (glutaraldehyde mass fraction 1%), and the reaction was stirred at room temperature for 3 hours, and then taken out and allowed to stand in air for 3 days, and then dried in an oven at 120°C for 24 hours to obtain solid glass beads with surface aldehyde groups.

[0047] 400 g of the surface aldehyde-modified solid glass microspheres were added into 4 L of the sulfur ylide solution, stirred at room temperature for 2 hours, then taken out and dried in air for 3 days, and finally surface epoxy-modified solid glass microspheres B were obtained.

[0048] [Preparation Example 3] Preparation of surface epoxy-modified glass microspheres C

[0049] 400 g of solid glass microspheres (Qinhuang, SGM-2) were added into 5 L of 1% dilute sulfuric acid, continuously stirred for 1 hour to remove the surface impurities of the solid glass microspheres, and then added into 3 L of 0.5% hydrofluoric acid solution, mixed and stirred at 60°C, and then left to stand for 2 h. The solid glass microspheres were taken out by filtration, washed with 1% sodium carbonate aqueous solution first, and then washed with deionized water for 5 times until the pH value of the washing liquid was in the range of 6-8. Then the obtained solid glass microspheres were vacuum dried at 80°C for 24 hours, and then added into 4800 g of glutaraldehyde potassium hydroxide aqueous solution (mass ratio of potassium hydroxide to water = 0.75:99.25) (mass fraction of glutaraldehyde 1%), stirred at room temperature for 3 hours, then taken out and dried in air for 3 days, and then placed in an oven at 120°C for drying for 24 hours, to obtain surface aldehyde-modified solid glass microspheres.

[0050] 400 g of the surface aldehyde-modified solid glass microspheres were added into 4 L of the sulfur ylide solution, stirred at room temperature for 2 hours, then taken out and dried in air for 3 days, and finally surface epoxy-modified solid glass microspheres C were obtained.

[0051] [Preparation Example 4] Preparation of surface silane-modified glass microspheres D

[0052] 400 g of solid glass microspheres (Sovitec, 050-20-215) were added into 5 L of 1% dilute sulfuric acid, continuously stirred for 1 hour to remove the surface impurities of the solid glass microspheres, and then added into 2 L of 0.5% hydrofluoric acid solution, mixed and stirred at 60°C, and then left to stand for 2 h. The solid glass microspheres were taken out by filtration, washed with 1% sodium carbonate aqueous solution first, and then washed with deionized water for 5 times until the pH value of the washing liquid was in the range of 6-8. Then the obtained solid glass microspheres were vacuum dried at 70°C for 24 hours. Then the obtained solid glass microspheres were added into 1 L of silane coupling agent KH-560 with a mass concentration of 1% for modification: stirred at room temperature for 2 h, suction filtered, and vacuum dried at 60°C for 24 h, to obtain surface silane-modified glass microspheres D.

[0053] [Example 1]

[0054] Put 426 g polycarbonate (Wanhua 2100), 250 g siloxane copolymer PC (out light FG1760), 2 g antioxidant 1076, 2 g antioxidant 168 and 20 g toughening agent M732 (Zhongyuan Chemical) into the main feeding port, 300 g surface epoxy modified glass bead A is added into the first side feeding port, after double screw extrusion granulation, dry for 4 h, polycarbonate composite material is obtained.

[0055] The double screw extrusion temperature is divided into eleven zones; the temperatures of the eleven zones are respectively: 260℃, 280℃, 285℃, 285℃, 285℃, 285℃, 285℃, 285℃, 280℃, 260℃, 260℃.

[0056]

Example 2

[0057] Put 646 g polycarbonate (Wanhua A1105), 150 g siloxane copolymer PC (Sanyuan ST6-3022PJ), 2 g antioxidant 1076, 2 g antioxidant 168 and 50 g toughening agent S-2001 (Mitsubishi Rayon) into the main feeding port, 150 g surface epoxy modified glass bead B is added into the first side feeding port, after double screw extrusion granulation, dry for 4 h, polycarbonate composite material is obtained.

[0058] The double screw extrusion temperature is divided into eleven zones; the temperatures of the eleven zones are respectively: 260℃, 280℃, 285℃, 285℃, 285℃, 285℃, 285℃, 285℃, 280℃, 260℃, 260℃.

[0059]

Example 3

[0060] Put 250 g polycarbonate (Teijin L-1250WP), 300 g siloxane copolymer PC (Wanhua, STC1720) into the main feeding port, 450 g surface epoxy modified glass bead C is added into the first side feeding port, after double screw extrusion granulation, dry for 4 h, polycarbonate composite material is obtained.

[0061] The double screw extrusion temperature is divided into eleven zones; the temperatures of the eleven zones are respectively: 260℃, 280℃, 285℃, 285℃, 285℃, 285℃, 285℃, 285℃, 280℃, 260℃, 260℃.

[0062]

Example 4

[0063] Put 850 g polycarbonate (Wanhua 2100), 100 g siloxane copolymer PC (out light FG1760) into the main feeding port, 50 g surface epoxy modified glass bead A is added into the first side feeding port, after double screw extrusion granulation, dry for 4 h, polycarbonate composite material is obtained.

[0064] The twin-screw extrusion temperature is divided into eleven zones; the temperatures of the eleven zones are 260℃, 280℃, 285℃, 285℃, 285℃, 285℃, 285℃, 285℃, 280℃, 260℃, 260℃, respectively.

[0065] Example 5

[0066] Add 396g polycarbonate (Wanhua 2100), 300g siloxane copolymer PC (Outlook FG1760), 2g antioxidant 1076, 2g antioxidant 168 and 150g toughening agent 1180AC (Dupont) from the main feeding port, add 150g surface epoxy modified glass beads A from the first side feeding port, after twin-screw extrusion granulation, dry for 4h, to obtain a polycarbonate composite material.

[0067] The twin-screw extrusion temperature is divided into eleven zones; the temperatures of the eleven zones are 260℃, 280℃, 285℃, 285℃, 285℃, 285℃, 285℃, 285℃, 280℃, 260℃, 260℃, respectively.

[0068] Example 6

[0069] Add 226g polycarbonate (Luxi Chemical LXTY1609), 450g siloxane copolymer PC (Outlook FG1760), 2g antioxidant 1076, 2g antioxidant 168 and 20g toughening agent 1330AC (Dupont) from the main feeding port, add 300g surface epoxy modified glass beads A from the first side feeding port, after twin-screw extrusion granulation, dry for 4h, to obtain a polycarbonate composite material.

[0070] The twin-screw extrusion temperature is divided into eleven zones; the temperatures of the eleven zones are 250℃, 270℃, 280℃, 280℃, 280℃, 280℃, 280℃, 280-285, 270℃, 250℃, 250℃, respectively.

[0071] Comparative Example 1

[0072] Add 426g polycarbonate (Wanhua 2100), 250g siloxane copolymer PC (Outlook FG1760), 2g antioxidant 1076, 2g antioxidant 168 and 20g toughening agent M732 (Zhongyuan Chemical) from the main feeding port, add 300g solid glass beads (Sovitec, 050-20-215) from the first side feeding port, after twin-screw extrusion granulation, dry for 4h, to obtain a polycarbonate composite material.

[0073] The twin-screw extrusion temperature is divided into eleven zones, and the temperatures of the eleven zones are 260℃, 280℃, 285℃, 285℃, 285℃, 285℃, 285℃, 285℃, 280℃, 260℃, and 260℃, respectively.

[0074]

Comparative Example 2

[0075] 426 g of polycarbonate (Wanhua 2100), 250 g of siloxane copolymer PC (Outlook FG1760), 2 g of antioxidant 1076, 2 g of antioxidant 168 and 20 g of toughening agent M732 (Zhongyuan Chemical) were added from the main feeding port, 300 g of surface silane modified glass beads D were added from the first side feeding port, and after twin-screw extrusion granulation, drying for 4 h, a polycarbonate composite material was obtained.

[0076] The twin-screw extrusion temperature is divided into eleven zones, and the temperatures of the eleven zones are 260℃, 280℃, 285℃, 285℃, 285℃, 285℃, 285℃, 285℃, 280℃, 260℃, and 260℃, respectively.

[0077] Table 1 is the test results of the tensile strength, 23℃ notched impact strength, density, dynamic friction coefficient and the like of the polycarbonate composite materials described in Comparative Examples 1-2 and Examples 1-6.

[0078] Table 1, test results

[0079]

[0080] By comparing Example 1 and Comparative Example 2, it can be found that the polycarbonate composite material prepared by using surface epoxy modified glass beads has higher interfacial strength between the surface epoxy modified glass beads and the polycarbonate matrix compared with the polycarbonate composite material prepared by using surface silane modified glass beads, so that the polycarbonate composite material has higher tensile strength and impact strength, and better wear resistance, and further improves the comprehensive performance of the material.

[0081] From the comparison of Examples 1-6, it can be seen that when the content of the surface epoxy modified glass beads in the polycarbonate composite material increases, the material strength and modulus tend to be improved, but the toughness decreases; when the content of the siloxane copolymer PC in the polycarbonate composite material increases, the dynamic friction coefficient and toughness of the material tend to be improved, and the strength slightly decreases. Therefore, the raw material composition and ratio in the formulation of the present application can obtain a polycarbonate composite material with excellent comprehensive performance.

[0082] The above only describes the preferred embodiments of the present application, and it should be pointed out that for those skilled in the art, without departing from the method of the present application, a number of improvements and supplements can be made, and these improvements and supplements should also be considered as the protection scope of the present application.

Claims

1. A polycarbonate composite material, characterized by, It is made of the following components in mass percentage: The surface epoxy-modified glass microbeads have a true density of 2.3-2.7 g / cm 3 , and a particle size of 5-180 μm. The preparation method of the surface epoxy modified glass beads comprises the following steps: A. Glass beads are added to a strong acid solution for surface roughening and hydroxylation; B. The surface hydroxylated glass beads prepared in step A are added to an aldehyde group solution of glutaraldehyde to perform surface aldehyde group modification: C. A DMSO solution of sulfur ylide is prepared; D. The surface aldehyde group modified glass beads prepared in step B are added to the solution prepared in step C to obtain surface epoxy modified glass beads.

2. The polycarbonate composite of claim 1, wherein, It is made of the following components in mass percentage:

3. The polycarbonate composite of claim 1, wherein, The toughening agent is selected from one or more of POE, POE-g-GMA, POE-g-MAH, EVA, ACR, EVA-g-GMA grafted polymer, SBS-g-GMA grafted polymer, MBS, SBS, EPR, EPDM, silicon-based toughening agent, and EMA.

4. The polycarbonate composite of claim 3, wherein, The toughening agent is one or more of MBS, silicon-based toughening agent, and EMA.

5. The polycarbonate composite of claim 1, wherein, The siloxane copolymer PC is a copolymer of bisphenol A and polydimethylsiloxane, and the weight average molecular weight of the copolymer is 18000-26000 g / mol, wherein the content of polydimethylsiloxane is 1-60%.

6. The polycarbonate composite of claim 5, wherein, In the siloxane copolymer PC, the content of polydimethylsiloxane is 5-20%.

7. The polycarbonate composite of claim 1, wherein, The weight average molecular weight of the polycarbonate is 22000-24000 g / mol.

8. The polycarbonate composite of any one of claims 1-7, wherein, The antioxidant is selected from phosphite and / or hindered phenolic antioxidant.

9. The polycarbonate composite of claim 8, wherein, The antioxidant is one or more of antioxidants 168, 626, B900, S-9228, 686, 1076, 1010.

10. A process for the production of a polycarbonate composite material as claimed in any of claims 1 to 9, characterized in that It comprises the following steps: The polycarbonate, surface epoxy modified glass beads, toughening agent, siloxane copolymer PC, and antioxidant are premixed and then extruded and granulated through a twin-screw extruder.

11. The method of making a polycarbonate composite of claim 10, wherein, The extrusion temperature of the twin-screw extruder is divided into eleven zones, which are 250-260℃, 270-280℃, 280-285℃, 280-285℃, 280-285℃, 280-285℃, 280-285℃, 280-285℃, 270-280℃, 250-260℃, and 250-260℃, respectively.

12. The method of making a polycarbonate composite of claim 10, wherein, The specific process of step A is as follows: The glass beads are first added to dilute sulfuric acid to remove surface impurities, then added to a hydrofluoric acid solution and stirred at room temperature for 1-8 h, and the glass beads are filtered out; the glass beads are washed with an aqueous sodium carbonate solution and then with deionized water until the pH value of the washing liquid is in the range of 6-8, and then dried to obtain surface roughened and hydroxylated glass beads.

13. The method of making a polycarbonate composite of claim 10, wherein, The specific process of step B is as follows: The surface hydroxylated glass beads prepared in step A are added to an aldehyde group solution of glutaraldehyde, heated to 50-70℃ and stirred for 1-10 h, then filtered out and dried to obtain surface aldehyde group modified glass beads.

14. The method of making a polycarbonate composite of claim 10, wherein, The specific process of step C is as follows: Dimethyl sulfide and iodomethane are added to a DMSO solution of sodium hydroxide or potassium hydroxide, stirred at 0-10℃ for 1-10 h, then sodium amide is added in multiple portions, and the stirring is continued for 0.5-2 h to obtain a DMSO solution of sulfur ylide.

15. The method of making a polycarbonate composite of claim 10, wherein, The specific process of the step D is: The surface aldehyde group modified glass beads prepared in step B are added into the solution prepared in step C, and the reaction is stirred at room temperature for 1-10 h, and then filtered and dried to obtain the epoxy modified glass beads.

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