CN113563711B - Toughened scratch-resistant polycarbonate material and preparation method and application thereof - Google Patents
Toughened scratch-resistant polycarbonate material and preparation method and application thereof Download PDFInfo
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Abstract
The application relates to the field of polycarbonate, and particularly discloses a toughened scratch-resistant polycarbonate material as well as a preparation method and application thereof. The toughened scratch-resistant polycarbonate material is prepared from the following raw materials in percentage by weight: 40-60% of a first polycarbonate; 36-50% of a second polycarbonate; 3.5-10% of a toughening agent; 0.5-3% of scratch-resistant agent; 0-4% of other auxiliary agents; wherein the second polycarbonate is a polydimethylsiloxane copolymeric polycarbonate, the second polycarbonate has a melt index greater than the melt index of the first polycarbonate, and the melt index of the second polycarbonate differs from the melt index of the first polycarbonate by from 2g/10min to 6g/10 min. The toughened scratch-resistant polycarbonate material has the advantage of meeting the requirements for improving the low-temperature toughness and scratch resistance of polycarbonate.
Description
Technical Field
The application relates to the field of polycarbonate, in particular to a toughened scratch-resistant polycarbonate material and a preparation method and application thereof.
Background
Along with the improvement of people's safety consciousness and the requirement of taking security precautions against in the production life is tight, the quality of safety protection article is also constantly promoting, and safety helmet has the important function of protection head as one of safety protection article, absorbs the collision energy, can reduce external impact to the injury of wearer to satisfy safety protection's needs.
The shell of the helmet is the core for the protective performance of the helmet, and the material of the shell of the helmet is various, wherein polycarbonate is commonly used, polycarbonate is abbreviated as PC, polycarbonate is a high molecular polymer containing carbonate groups in molecular chains, and has good strength and elastic coefficient and good heat aging resistance, so the shell of the helmet is often used as a material for resisting external impact, but for an unmodified polycarbonate material, the low-temperature toughness is poor, and the safety grade of the polycarbonate as the helmet is influenced.
In order to improve the problem of poor low-temperature toughness of polycarbonate, manufacturers usually add a toughening agent to enhance the low-temperature toughness, but since the performance of the polycarbonate to be improved is not only one of the low-temperature toughness, manufacturers add other additives to obtain other performances, for example, add a scratch-resistant agent to improve the scratch-resistant performance, however, in actual production, it is found that if the toughening agent and the scratch-resistant agent are added simultaneously, the improvement range of the low-temperature toughness and the scratch-resistant performance is far lower than that when one additive is added separately, and the requirement is difficult to meet.
Disclosure of Invention
In order to meet the requirements for improving the low-temperature toughness and the scratch resistance of polycarbonate, the application provides a toughened scratch-resistant polycarbonate material and a preparation method and application thereof.
In a first aspect, the application provides a toughened scratch-resistant polycarbonate material, which adopts the following technical scheme:
the toughened scratch-resistant polycarbonate material is prepared from the following raw materials in percentage by weight:
40-60% of a first polycarbonate;
36-50% of a second polycarbonate;
3.5-10% of a toughening agent;
0.5-3% of scratch-resistant agent;
0-4% of other auxiliary agents;
wherein the second polycarbonate is a polydimethylsiloxane copolymeric polycarbonate, the second polycarbonate has a melt index greater than the melt index of the first polycarbonate, and the melt index of the second polycarbonate differs from the melt index of the first polycarbonate by from 2g/10min to 6g/10 min.
The polycarbonate has huge benzene rings and high rigidity, so that the acting force among polycarbonate molecules is large, the molecular chain binding force in the polycarbonate is strong, and the molecular chain is not easy to slip under the action of external force, so that the external additive is difficult to be well compatible with a polycarbonate matrix after the addition amount or variety of the external additive is increased, and the effect to be achieved by the external additive is difficult to exert.
By adopting the technical scheme, dimethyl silicone polymer copolymerized polycarbonate is mixed in a polycarbonate system, and the silicon copolymerized PC is cooperated with the toughening agent and the scratch-resistant agent, so that the low-temperature toughness and the scratch-resistant performance of the material are improved.
The first polycarbonate is common polycarbonate, the rigidity of benzene rings of the polydimethylsiloxane copolymerized polycarbonate is weakened due to the action of polydimethylsiloxane, the flexibility of molecular chains is improved, and the flexibility of the whole polycarbonate matrix can be improved by adopting a compounding mode of the common polycarbonate and the polydimethylsiloxane copolymerized polycarbonate, so that the toughening agent and the scratch-resistant agent can be smoothly blended into the polycarbonate matrix; in addition, because the surface hydrophobicity of the polydimethylsiloxane copolymerized polycarbonate is high, the compatibility of the polycarbonate to the toughening agent and the scratch resistant agent can be improved, and the performances of the toughening agent and the scratch resistant agent are further exerted.
This application improves the thickness degree of consistency of material through the difference of the melt index of controlling first polycarbonate and second polycarbonate and the quantity of first polycarbonate and second polycarbonate to improve the dispersion degree of toughening agent and resistant scraping agent, and then exert the performance of toughening agent and resistant scraping agent, improve low temperature toughness and resistant scraping nature.
Optionally, the weight ratio of the first polycarbonate to the second polycarbonate is (1.2-1.36): 1.
By adopting the technical scheme, the compounding proportion of the common polycarbonate and the polydimethylsiloxane copolymerized polycarbonate can keep the flexibility of the polycarbonate matrix in the optimal range, thereby not only keeping the material strength, but also improving the low-temperature toughness.
Optionally, the weight ratio of the second polycarbonate to the toughening agent to the scratch-resistant agent is (20-24): (5-6): 1.
By adopting the technical scheme, the proportion of the second polycarbonate, the toughening agent and the scratch-resistant agent is controlled, the functions of the toughening agent and the scratch-resistant agent are further exerted, and the improvement degree of the low-temperature toughness is larger.
Optionally, the melt index of the first polycarbonate is 6g/10 min-8 g/10min, and the melt index of the second polycarbonate is 8g/10 min-12 g/10 min; preferably, the first polycarbonate has a melt index of 7g/10min to 8g/10min, and the second polycarbonate has a melt index of 9g/10min to 10g/10 min.
By adopting the technical scheme, the melt indexes of the common polycarbonate and the polydimethylsiloxane copolymerized polycarbonate are controlled, so that the melt indexes of the common polycarbonate and the polydimethylsiloxane copolymerized polycarbonate are similar and kept at a moderate level, the thickness uniformity of the polycarbonate material is improved, and the low-temperature toughness and the scratch resistance are improved.
Optionally, the toughening agent is selected from one or more of ABS high-rubber powder, methyl methacrylate-butadiene-styrene copolymer, ethylene-butyl acrylate copolymer, butyl acrylate-methyl methacrylate copolymer and ethylene-methacrylate copolymer; the scratch-resistant agent is selected from one or more of erucamide, silicone master batch and talcum powder.
By adopting the technical scheme, the specific toughening agent type and the scratch resistance agent type can effectively improve the low-temperature toughness and the scratch resistance.
Optionally, the toughening agent comprises a methyl methacrylate-butadiene-styrene copolymer, an ethylene-butyl acrylate copolymer and an ethylene-methacrylate copolymer, the weight ratio of the methyl methacrylate-butadiene-styrene copolymer to the ethylene-butyl acrylate copolymer to the ethylene-methacrylate copolymer is 1 (0.5-0.8) (0.3-0.5), the scratch-resistant agent comprises erucamide and silicone master batches, and the weight ratio of the erucamide to the silicone master batches is 1 (0.3-0.6).
By adopting the technical scheme, the methyl methacrylate-butadiene-styrene copolymer, the ethylene-butyl acrylate copolymer and the ethylene-methacrylate copolymer are synergistic, and the specific use proportion of the erucamide and the silicone master batch is matched, so that the low-temperature toughness and the scraping resistance are improved, the structural uniformity of the material is improved, the coordination of each part of the material is higher, the heat-resistant stability is improved, and the overall performance of the material is more excellent.
Optionally, the other auxiliary agents are selected from one or more of an antioxidant, an anti-ultraviolet agent and a color masterbatch; preferably, the antioxidant is selected from two of antioxidant 1010, antioxidant 168 and antioxidant DLTP; or the uvioresistant agent is an ultraviolet absorbent UV-P.
By adopting the technical scheme, the oxidation resistance and the ultraviolet resistance of the material are improved, and the stability of the material is improved.
In a second aspect, the application provides a preparation method of a toughened scratch-resistant polycarbonate material, which adopts the following technical scheme:
a preparation method of a toughened scratch-resistant polycarbonate material comprises the following steps:
s1, mixing and stirring first polycarbonate, second polycarbonate, a toughening agent, a scratch-resistant agent and other auxiliaries to obtain a mixture;
s2, carrying out double-screw co-directional kneading and blending extrusion on the mixture at the temperature of 220-250 ℃, filtering, shearing and preplasticizing, extruding and plasticizing, casting, cooling and shaping to obtain the toughened scratch-resistant polycarbonate material.
By adopting the technical scheme, because the polydimethylsiloxane copolymerized polycarbonate is added, the flexibility of the whole polycarbonate matrix is improved, the steps of extrusion granulation, drying and remelting extrusion in a general process can be omitted, and a double-screw co-directional kneading and plasticizing mode is adopted to obtain the polycarbonate material with better dispersion uniformity of the toughening agent and the scratch-resistant agent.
Optionally, in the step S2, the first zone temperature of the twin-screw extrusion is 220 to 230 ℃, the second zone temperature is 240 to 250 ℃, the third zone temperature is 240 to 250 ℃, the fourth zone temperature is 240 to 250 ℃, the fifth zone temperature is 240 to 250 ℃, and the screw rotation speed is 60 to 80 r/min.
By adopting the technical scheme, the double-screw extrusion temperature setting is favorable for improving the mixing uniformity of the polycarbonate and other raw materials.
Optionally, in the step S2, a three-roll calender is used for casting, the temperature of the first press roll is 120-123 ℃, the temperature of the second press roll is 120-125 ℃, the temperature of the third press roll is 125-130 ℃, the rotation speeds of the three press rolls are all 25-35 r/min, and the winding tension is 380-400N.
By adopting the technical scheme, the condition that the local internal stress of the polycarbonate material is overlarge due to quenching can be reduced by hot pressing of the three-roller calender, the temperature of the three press rollers and the rolling tension and speed are controlled, the uniformity of each part of the material is improved, and the low-temperature toughness and the scraping resistance are improved.
In a third aspect, the application provides an application of a toughened scratch-resistant polycarbonate material, which adopts the following technical scheme:
the application of the toughened scratch-resistant polycarbonate material is to prepare the helmet shell material by carrying out plastic suction molding on the toughened scratch-resistant polycarbonate material.
By adopting the technical scheme, the high-strength, good-low-temperature-toughness and scratch-resistant helmet shell is obtained, the helmet quality is improved, and the safety of a wearer is protected.
In summary, the present application has the following beneficial effects:
1. because the polydimethylsiloxane copolymerized polycarbonate is mixed in the material adopted by the method, the polydimethylsiloxane copolymerized polycarbonate is cooperated with the toughening agent and the scratch-resistant agent, the overall flexibility of the polycarbonate matrix is improved, so that the toughening agent and the scratch-resistant agent can be smoothly blended into the polycarbonate matrix, the compatibility of the polycarbonate overall to the toughening agent and the scratch-resistant agent is improved, and the low-temperature toughness and the scratch-resistant performance of the material are improved by controlling the melt indexes of the two polycarbonates.
2. In the application, the methyl methacrylate-butadiene-styrene copolymer, the ethylene-butyl acrylate copolymer and the ethylene-methacrylate copolymer are preferably compounded for use, and the erucamide and the silicone master batch are used in a synergistic manner, so that the low-temperature toughness and the scratch resistance of the material are improved, and meanwhile, the thermal stability is improved.
3. According to the method, the material with good uniformity is obtained by the mode of co-rotating kneading and extruding the double screws and the addition of the polydimethylsiloxane copolymerized polycarbonate, so that the low-temperature toughness and the scratch resistance of the material are improved.
Detailed Description
The present application will be described in further detail with reference to examples.
The first polycarbonate is selected from the company Diurena Japan and has a melt index of 6g/10min to 8g/10 min;
the second polycarbonate is selected from polydimethylsiloxane copoly polycarbonate of Sabourne basic industry company, and the melt index is 8g/10 min-14 g/10 min;
methylmethacrylate-butadiene-styrene copolymer was selected from korean LG chemical, model EM 500A;
ethylene-butyl acrylate copolymer was selected from arkema, france, model 17BA 07N;
ethylene-methacrylate copolymers were selected from arkema, france, model No. AX 8900;
erucamide was selected from the British Poa Inc. model Crodamide ER-CH;
antioxidant 1010 and antioxidant 168 were selected from yabao, usa;
the UV-P absorber was purchased from Suqian Liangsheng technology.
The above mentioned manufacturer's models are used to support the solution of the present application for completeness of disclosure and are not limited to the listed manufacturer's models.
Examples
Example 1
A toughened scratch-resistant polycarbonate material is prepared from the following raw materials:
60kg of first polycarbonate with the melt index of 6g/10min, 36kg of second polycarbonate with the melt index of 8g/10min, 3.5kg of toughening agent and 0.5kg of scratch-resistant agent, wherein the toughening agent is methyl methacrylate-butadiene-styrene copolymer, and the scratch-resistant agent is erucamide.
A preparation method of a toughened scratch-resistant polycarbonate material comprises the following steps:
s1, respectively drying the first polycarbonate and the second polycarbonate at the drying temperature of 120 ℃ for 2h, and then putting the first polycarbonate, the second polycarbonate, the toughening agent and the scratch-resistant agent into a high-speed stirrer at the stirring speed of 1000r/min for 10min to obtain a mixture.
S2, putting the mixture into a meshing co-rotating double-screw extruder, wherein the first-zone temperature of the double-screw extruder is 210 ℃, the second-zone temperature is 230 ℃, the third-zone temperature is 230 ℃, the fourth-zone temperature is 230 ℃ and the fifth-zone temperature is 230 ℃, the screw rotating speed is 60r/min, blending and extruding the mixture in the double-screw extruder, filtering the mixture by a filter screen, shearing and pre-plasticizing the mixture, extruding the mixture into a die head, the die head temperature is 240 ℃, further plasticizing the mixture, then putting the mixture into a three-roller calender for tape casting, the temperature of a first compression roller is 115 ℃, the temperature of a second compression roller is 115 ℃, the temperature of a third compression roller is 115 ℃, the rotating speed of the three compression rollers is 30r/min, rolling tension is 450N, cooling and shaping are carried out after the tape casting is finished, and slicing is carried out, so that the toughened scratch-resistant polycarbonate material is obtained.
Examples 2 to 9
Examples 2 to 9 are different from example 1 in the raw materials and the compounding ratio, and are shown in table 1.
TABLE 1
| First polycarbonate (kg) | Second polycarbonate (kg) | First polycarbonate melt index (g/10min) | Second polycarbonate melt index (g/10min) | Flexibilizer (kg) | Scratch-resistant agent (kg) | |
| Example 1 | 60.0 | 36.0 | 6 | 8 | 3.5 | 0.5 |
| Example 2 | 40.0 | 50.0 | 8 | 12 | 7.0 | 3.0 |
| Example 3 | 45.0 | 42.0 | 6 | 8 | 10.0 | 3.0 |
| Example 4 | 53.0 | 39.0 | 6 | 8 | 6.5 | 1.5 |
| Example 5 | 48.0 | 40.0 | 6 | 8 | 9.0 | 3.0 |
| Example 6 | 48.0 | 40.0 | 6 | 8 | 10.0 | 2.0 |
| Example 7 | 50.4 | 38.4 | 6 | 8 | 9.6 | 1.6 |
| Example 8 | 50.4 | 38.4 | 7 | 9 | 9.6 | 1.6 |
| Example 9 | 50.4 | 38.4 | 8 | 10 | 9.6 | 1.6 |
The toughening agent used in example 2 is an ethylene-butyl acrylate copolymer, and the scratch resistant agent is silicone master batch.
Example 10
This example differs from example 9 in that in this example, the toughening agent consisted of a methyl methacrylate-butadiene-styrene copolymer, an ethylene-butyl acrylate copolymer, and an ethylene-methacrylate copolymer, where the amount of methyl methacrylate-butadiene-styrene copolymer added was 3.2kg, the amount of ethylene-butyl acrylate copolymer added was 3.2kg, and the amount of ethylene-methacrylate copolymer added was 3.2 kg; the scratch-resistant agent consists of erucamide and silicone master batch, wherein the addition amount of the erucamide is 0.8kg, and the addition amount of the silicone master batch is 0.8 kg.
Example 11
This example differs from example 9 in that in this example, the toughening agent consisted of a methyl methacrylate-butadiene-styrene copolymer, an ethylene-butyl acrylate copolymer, and an ethylene-methacrylate copolymer, with the methyl methacrylate-butadiene-styrene copolymer being added in an amount of 5.3kg, the ethylene-butyl acrylate copolymer being added in an amount of 2.7kg, and the ethylene-methacrylate copolymer being added in an amount of 1.6 kg; the scratch-resistant agent consists of erucamide and silicone master batch, wherein the addition amount of the erucamide is 1.2kg, and the addition amount of the silicone master batch is 0.4 kg.
Example 12
This example differs from example 9 in that in this example, the toughening agent consisted of a methyl methacrylate-butadiene-styrene copolymer, an ethylene-butyl acrylate copolymer, and an ethylene-methacrylate copolymer, with the methyl methacrylate-butadiene-styrene copolymer being added in an amount of 4.2kg, the ethylene-butyl acrylate copolymer being added in an amount of 3.3kg, and the ethylene-methacrylate copolymer being added in an amount of 2.1 kg; the scratch-resistant agent consists of erucamide and silicone master batch, wherein the addition amount of the erucamide is 1kg, and the addition amount of the silicone master batch is 0.6 kg.
Example 13
This example is different from example 12 in that the twin-screw extruder has a first zone temperature of 220 deg.C, a second zone temperature of 250 deg.C, a third zone temperature of 250 deg.C, a fourth zone temperature of 250 deg.C and a fifth zone temperature of 250 deg.C in the step S2.
Example 14
The present example is different from example 12 in that in step S2, the temperature of the first roll of the three-roll calender is 120 ℃, the temperature of the second roll is 120 ℃, the temperature of the third roll is 125 ℃, the rotation speed of the three rolls is 30r/min, and the winding tension is 380N.
Example 15
The present example is different from example 12 in that in step S2, the temperature of the first roll of the three-roll calender is 123 ℃, the temperature of the second roll is 124 ℃, the temperature of the third roll is 130 ℃, the rotation speed of the three rolls is 30r/min, and the winding tension is 400N.
Example 16
The difference between this embodiment and embodiment 15 is that, in this embodiment, the toughened scratch-resistant polycarbonate material is made from the following raw materials:
48.4kg of first polycarbonate with the melt index of 8g/10min, 36.9kg of second polycarbonate with the melt index of 10g/10min, 4kg of methyl methacrylate-butadiene-styrene copolymer, 3.2kg of ethylene-butyl acrylate copolymer, 2kg of ethylene-methacrylate copolymer, 1kg of erucamide, 0.5kg of silicone master batch, 10100.8 kg of antioxidant, 1681.6 kg of antioxidant and 1.6kg of UV-P.
Example 17
The difference between this embodiment and embodiment 15 is that, in this embodiment, the toughened scratch-resistant polycarbonate material is made from the following raw materials:
50kg of first polycarbonate with the melt index of 8g/10min, 38kg of second polycarbonate with the melt index of 10g/10min, 4.2kg of methyl methacrylate-butadiene-styrene copolymer, 3.2kg of ethylene-butyl acrylate copolymer, 2kg of ethylene-methacrylate copolymer, 1kg of erucamide, 0.5kg of silicone master batch, 10100.2 kg of antioxidant, 1680.4 kg of antioxidant and 0.4kg of UV-P.
Comparative example
Comparative example 1
The comparative example directly adopts the first polycarbonate as the toughening scratch-resistant polycarbonate material, and the melt index of the first polycarbonate is 6g/10 min.
Comparative example 2
This comparative example differs from example 3 in that in this comparative example, the second polycarbonate is replaced by an equal amount of the first polycarbonate.
Comparative example 3
This comparative example differs from example 3 in that in this comparative example, the second polycarbonate is replaced by an equal amount of the first polycarbonate and the erucamide is replaced by an equal amount of the methyl methacrylate-butadiene-styrene copolymer.
Comparative example 4
This comparative example differs from example 3 in that in this comparative example the first polycarbonate was added in an amount of 23kg and the second polycarbonate was added in an amount of 64 kg.
Comparative example 5
This comparative example differs from example 3 in that in this comparative example the first polycarbonate has a melt index of 8g/10min and the second polycarbonate has a melt index of 8g/10 min.
Comparative example 6
This comparative example differs from example 3 in that in this comparative example the first polycarbonate has a melt index of 6g/10min and the second polycarbonate has a melt index of 14g/10 min.
Comparative example 7
The difference between the comparative example and the example 3 is that in the comparative example, the mixture is subjected to blending extrusion in a double-screw extruder, granulation and drying, and then is put into a single-screw extruder for melt extrusion.
Application examples
The toughened scratch-resistant polycarbonate materials prepared in the examples 1 to 17 and the comparative examples 1 to 7 of the application are respectively subjected to plastic suction forming to obtain helmet shell materials.
Performance test
The melt indices of the first polycarbonate and the second polycarbonate of the present application were determined by ISO 1133, with a melt index test temperature of 300 ℃ and a nominal load of 1.2 kg.
The toughened scratch-resistant polycarbonate materials prepared in examples 1-17 and comparative examples 1-7 of the application are respectively sliced to obtain samples with the length, the width and the thickness of 100mm and the thickness of 2mm, 12 samples are prepared in each example or comparative example, the samples are frozen at minus 30 ℃ for 4 hours and then subjected to a ball dropping test, 500g of steel balls are subjected to free falling from the height of 1.3m away from the samples, the surface condition of the samples after the steel balls hit the samples is observed, the low-temperature toughness of the materials is judged according to the result, and the test results are shown in table 2.
The toughened scratch-resistant polycarbonate materials prepared in examples 1 to 17 and comparative examples 1 to 7 of the present application were subjected to a scratch resistance test according to GB/T6739-.
The toughened scratch and mar resistant polycarbonate materials prepared in examples 1 to 17 and comparative examples 1 to 7 of the present application were subjected to a bending strength test according to ASTM D790, and the test results are shown in Table 3.
The toughened, scratch and mar resistant polycarbonate materials prepared in examples 1 to 17 and comparative examples 1 to 7 of the present application were subjected to a Vicat softening temperature test according to ISO306/B50, the test results being shown in Table 3.
TABLE 2
| Falling ball experiment | ||||
| Crushing (number of blocks) | Cracking (number of blocks) | Slight crack (number of blocks) | Intact (number of blocks) | |
| Example 1 | 2 | 5 | 3 | 2 |
| Example 2 | 2 | 4 | 4 | 2 |
| Example 3 | 2 | 3 | 5 | 2 |
| Example 4 | 1 | 2 | 5 | 4 |
| Example 5 | 0 | 3 | 5 | 4 |
| Example 6 | 0 | 2 | 5 | 5 |
| Example 7 | 0 | 2 | 4 | 6 |
| Example 8 | 0 | 1 | 5 | 6 |
| Example 9 | 0 | 2 | 3 | 7 |
| Example 10 | 0 | 1 | 4 | 7 |
| Example 11 | 0 | 1 | 3 | 8 |
| Example 12 | 0 | 1 | 3 | 8 |
| Example 13 | 0 | 0 | 2 | 10 |
| Example 14 | 0 | 0 | 1 | 11 |
| Example 15 | 0 | 0 | 1 | 11 |
| Example 16 | 0 | 0 | 0 | 12 |
| Example 17 | 0 | 0 | 1 | 11 |
| Comparative example 1 | 9 | 3 | 0 | 0 |
| Comparative example 2 | 6 | 5 | 1 | 0 |
| Comparative example 3 | 4 | 4 | 3 | 1 |
| Comparative example 4 | 4 | 3 | 3 | 2 |
| Comparative example 5 | 3 | 4 | 4 | 1 |
| Comparative example 6 | 4 | 4 | 3 | 1 |
| Comparative example 7 | 2 | 7 | 2 | 1 |
TABLE 3
| Hardness of | Flexural Strength (MPa) | Vicat softening temperature (. degree. C.) | |
| Example 1 | 2H | 94.7 | 151 |
| Example 2 | 2H | 94.8 | 151 |
| Example 3 | 2H | 95.2 | 150 |
| Example 4 | 2H | 95.6 | 151 |
| Example 5 | 2H | 95.0 | 151 |
| Example 6 | 2H | 95.8 | 152 |
| Example 7 | 2H | 95.5 | 151 |
| Example 8 | 3H | 95.6 | 151 |
| Example 9 | 3H | 95.5 | 151 |
| Example 10 | 3H | 95.8 | 152 |
| Example 11 | 3H | 96.0 | 158 |
| Example 12 | 3H | 96.6 | 158 |
| Example 13 | 3H | 96.0 | 158 |
| Example 14 | 3H | 96.5 | 157 |
| Example 15 | 3H | 96.4 | 158 |
| Example 16 | 3H | 96.7 | 159 |
| Example 17 | 3H | 96.8 | 158 |
| Comparative example 1 | 2B | 90.5 | 148 |
| Comparative example 2 | 2B | 93.2 | 151 |
| Comparative example 3 | 2B | 93.8 | 151 |
| Comparative example 4 | 2B | 87.8 | 150 |
| Comparative example 5 | B | 91.5 | 150 |
| Comparative example 6 | B | 92.1 | 151 |
| Comparative example 7 | HB | 94.1 | 152 |
According to tables 2 and 3, in example 3, compared with comparative example 1, after polydimethylsiloxane copolycarbonate, a toughening agent and a scratch resistance agent are added on the basis of common polycarbonate, the low-temperature toughness and the scratch resistance of the polycarbonate material are both greatly improved; compared with the comparative example 2, the low-temperature toughness of the polycarbonate material is improved after only the toughening agent and the scratch resistance agent are added on the basis of the common polycarbonate, but the scratch resistance is not improved, and the improvement range of the low-temperature toughness is small, which shows that when the toughening agent and the scratch resistance agent are used for improving the low-temperature toughness and the scratch resistance, the low-temperature toughness and the scratch resistance are obviously improved by being matched with the polydimethylsiloxane copolymerized polycarbonate.
Comparative example 2 compared to comparative example 3, the low temperature toughness of the polycarbonate material with only the addition of the toughening agent polydimethylsiloxane copolycarbonate was superior to the low temperature toughness of the polycarbonate material with both the toughening agent and the scratch resistance agent added, when the polydimethylsiloxane copolycarbonate was not added.
In example 3, compared with comparative example 4, when the weight percentage of the common polycarbonate is 40-60% and the weight percentage of the polydimethylsiloxane copolymerized polycarbonate is 36-50%, the low-temperature toughness and the scratch resistance are better, and the bending strength can be improved.
Compared with comparative examples 5-6, when the difference between the melt indexes of the common polycarbonate and the polydimethylsiloxane copolymerized polycarbonate is 2-6 g/10min, the blending effect of the common polycarbonate and the polydimethylsiloxane copolymerized polycarbonate is better, so that the low-temperature toughness and the scratch resistance are better.
Example 3 compared with comparative example 7, the method of using twin-screw co-kneading not only saves the tedious steps of extrusion granulation, drying and remelting extrusion, but also improves the low-temperature toughness and scratch resistance to a certain extent.
Compared with the embodiment 3, when the weight ratio of the common polycarbonate to the polydimethylsiloxane copolycarbonate is 1.2-1.36, the low-temperature toughness of the material is improved; in examples 6 to 7, compared with example 5, when the weight ratio of the polydimethylsiloxane copolycarbonate to the toughening agent to the scratch resistant agent is (20-24): 5-6): 1, the low-temperature toughness of the material is further improved.
Examples 8-9 compared with example 7, when the melt index of the conventional polycarbonate was 7g/10min, the melt index of the polydimethylsiloxane copolymeric polycarbonate was 9g/10min, and the melt index of the conventional polycarbonate was 8g/10min and the melt index of the polydimethylsiloxane copolymeric polycarbonate was 10g/10min, both the low temperature toughness and the scratch resistance of the material were improved.
Compared with the example 9, the examples 10 to 12 further select three specific toughening agents and two specific scratch-resistant agents, and limit the mixture ratio, so that not only can the low-temperature toughness be improved, but also the Vicat softening temperature can be greatly improved, and the thermal stability of the material is improved.
Compared with the embodiment 12, the embodiments 13-15 can further improve the low-temperature toughness by adjusting the temperature of the twin-screw extrusion zone and the temperature difference of three press rolls of a three-roll calender, thereby improving the performance of the material.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A toughened scratch-resistant polycarbonate material is characterized in that: the material is prepared from the following raw materials in percentage by weight:
40-60% of a first polycarbonate;
36-50% of a second polycarbonate;
3.5-10% of a toughening agent;
0.5-3% of scratch-resistant agent;
0-4% of other auxiliary agents;
wherein the second polycarbonate is a polydimethylsiloxane co-polycarbonate, the second polycarbonate has a melt index greater than the melt index of the first polycarbonate, and the melt index of the second polycarbonate differs from the melt index of the first polycarbonate by from 2g/10min to 6g/10 min;
the first polycarbonate has a melt index of 6g/10 min-8 g/10min, and the second polycarbonate has a melt index of 8g/10 min-12 g/10 min;
the toughening agent is selected from one or more of ABS high glue powder, methyl methacrylate-butadiene-styrene copolymer, ethylene-butyl acrylate copolymer, butyl acrylate-methyl methacrylate copolymer and ethylene-methacrylate copolymer; the scratch-resistant agent is selected from one or more of erucamide, silicone master batch and talcum powder.
2. The toughened scratch resistant polycarbonate material of claim 1, wherein: the weight ratio of the first polycarbonate to the second polycarbonate is (1.2-1.36): 1.
3. The toughened, scratch resistant polycarbonate material of claim 1 or 2, wherein: the weight ratio of the second polycarbonate to the toughening agent to the scratch-resistant agent is (20-24) to (5-6) to 1.
4. The toughened scratch resistant polycarbonate material of claim 1, wherein: the toughening agent comprises a methyl methacrylate-butadiene-styrene copolymer, an ethylene-butyl acrylate copolymer and an ethylene-methacrylate copolymer, the weight ratio of the methyl methacrylate-butadiene-styrene copolymer to the ethylene-butyl acrylate copolymer to the ethylene-methacrylate copolymer is 1 (0.5-0.8) to 0.3-0.5, the scratch-resistant agent comprises erucamide and silicone master batches, and the weight ratio of the erucamide to the silicone master batches is 1 (0.3-0.6).
5. A preparation method of the toughened scratch-resistant polycarbonate material is characterized by comprising the following steps of:
s1, mixing and stirring first polycarbonate, second polycarbonate, a toughening agent, a scratch-resistant agent and other auxiliaries to obtain a mixture;
s2, carrying out double-screw co-directional kneading and blending extrusion on the mixture at the temperature of 220-250 ℃, filtering, shearing and preplasticizing, extruding and plasticizing, casting, cooling and shaping to obtain the toughened scratch-resistant polycarbonate material.
6. The preparation method of the toughened scratch-resistant polycarbonate material as claimed in claim 5, wherein: in the step S2, the first zone temperature of the twin-screw extrusion is 220-230 ℃, the second zone temperature is 240-250 ℃, the third zone temperature is 240-250 ℃, the fourth zone temperature is 240-250 ℃, the fifth zone temperature is 240-250 ℃, and the screw rotation speed is 60-80 r/min.
7. The preparation method of the toughened scratch-resistant polycarbonate material as claimed in claim 5, wherein: in the step S2, a three-roll calender is adopted for casting, the temperature of the first press roll is 120-123 ℃, the temperature of the second press roll is 120-125 ℃, the temperature of the third press roll is 125-130 ℃, the rotating speed of the three press rolls is 25-35 r/min, and the winding tension is 380-400N.
8. The application of the toughened scratch-resistant polycarbonate material is characterized in that: the helmet shell material is made by plastic molding the toughened scratch-resistant polycarbonate material as claimed in any one of claims 1 to 4.
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| CN109971150A (en) * | 2019-04-25 | 2019-07-05 | 金旸（厦门）新材料科技有限公司 | A kind of scratch-resistant for luggage shell is cold-resistant to be exempted to spray PC material and preparation method thereof |
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