CN111484719A - High-impact-resistance flame-retardant reinforced polycarbonate composite material and preparation method thereof - Google Patents
High-impact-resistance flame-retardant reinforced polycarbonate composite material and preparation method thereof Download PDFInfo
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- CN111484719A CN111484719A CN201910986844.0A CN201910986844A CN111484719A CN 111484719 A CN111484719 A CN 111484719A CN 201910986844 A CN201910986844 A CN 201910986844A CN 111484719 A CN111484719 A CN 111484719A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention discloses a high-impact-resistance flame-retardant reinforced polycarbonate composite material and a preparation method thereof. The polycarbonate composite material comprises the following components in parts by weight: 72.8-88.9 parts of polycarbonate; 10-20 parts of glass fiber filler; coupling agent: 0.3-0.8 part; a toughening agent: 3.0-7.0 parts; flame retardant: 0.2-1.0 part; anti-dripping agent: 0.1-0.5 part; 0.4-1.0 part of antioxidant; 0.2-1.0 part of lubricant. The glass fiber reinforced polycarbonate composite material has the advantages that the prepared glass fiber reinforced polycarbonate composite material has the characteristics of high impact resistance and high flame retardance, meets the requirements of materials in the electronic and electrical industry, can improve the mechanical strength of parts and achieve the effects of high impact resistance and high flame retardance, can achieve more ideal rigidity and toughness balance compared with the traditional glass fiber reinforced polycarbonate, and is simple in preparation process, low in cost and easy for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high-impact-resistance flame-retardant reinforced polycarbonate composite material and a preparation method thereof.
Background
Polycarbonate has excellent mechanical properties, dimensional stability, transparency, weather resistance and other characteristics, and is widely applied to the fields of automobile industry, electronics, electrical and office equipment and the like, but has the defects of poor molding processability, easy stress cracking, poor notch sensitivity and the like, glass fiber has the advantages of high tensile strength, large impact absorption capacity, good elastic coefficient, good heat resistance, low price and the like, is often used as a reinforcing phase to prepare composite materials such as polymers, rubber and the like, a single polycarbonate resin hardly meets various requirements, and in order to obtain a polycarbonate material with excellent mechanical properties, the glass fiber is modified to obviously improve the mechanical properties such as tensile strength, bending modulus and the like, and also can improve the properties such as dimensional stability, heat resistance, friction resistance and the like, so that the polycarbonate material is applied to the fields of mechanical properties, electrical and electronic equipment, The method is widely applied to the fields of instruments, electronic appliances and the like.
The glass fiber reinforced polycarbonate has the main problems that the glass fiber filled and modified polycarbonate improves the tensile strength, the bending modulus, the compressive strength and the wear resistance of the material, reduces the water absorption, the creep deformation, the molding shrinkage and other properties, but the impact resistance of the polycarbonate is obviously reduced because the impact property of the polycarbonate is sensitive to glass fiber fillers, so that the application range of the glass fiber polycarbonate composite material is limited, and the polycarbonate has certain flame retardance, the oxygen index is 21-24 parts, and the flame retardance reaches the level of U L94V-2, but the flame retardance of the polycarbonate can be reduced by adding the glass fiber, so that a higher flame retardance grade is achieved, the requirements of various fields, particularly the fields of electronic and electric appliances on the polycarbonate material are met, and the polycarbonate must be subjected to flame retardance modification.
In view of the above, there is a need for a high impact resistant and flame retardant reinforced polycarbonate composite material.
Disclosure of Invention
The invention overcomes the defects in the prior art, provides a high-impact-resistance flame-retardant reinforced polycarbonate composite material, which has the characteristics of high impact resistance, high flame retardance and high strength, meets the requirements of materials in the field of electronic and electric appliances, can achieve more ideal rigidity-toughness balance compared with the traditional polycarbonate, has simple preparation process and lower cost, and is easy to carry out large-scale industrial production, and the technical scheme adopted by the invention is as follows:
the raw materials are calculated according to the mass fraction, and the detailed formula is as follows:
72.8-88.9 parts of polycarbonate
10-20 parts of glass fiber filler
Coupling agent: 0.3 to 0.8 portion
A toughening agent: 3.0 to 7.0 parts
Flame retardant: 0.2 to 1.0 portion
Antioxidant: 0.4 to 1.0 portion
Lubricant: 0.2 to 1.0 portion.
1. The polycarbonate is at least one polycarbonate composition. The melt index of the polycarbonate is 10-30g/10min (300 ℃, 1.2 Kg).
2. The glass fiber filler is at least one of alkali glass fiber, alkali-free glass fiber, high-strength glass fiber and chemical-resistant glass fiber.
3. The coupling agent is composed of at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent.
4. The toughening agent is composed of at least one of methyl acrylate-butadiene-styrene copolymer (MBS), ethylene-methyl acrylate copolymer (EMA) and styrene-maleic anhydride copolymer (SMA).
5. The flame retardant is composed of at least one of organic phosphorus, silicon, sulfonate and PTFE.
6. The antioxidant is prepared by compounding hindered phenol antioxidant and phosphite antioxidant according to the proportion of 1: 1.
7. The lubricant is one or more of polyethylene wax, polycarbonate wax, calcium stearate, EBS and TAF.
8. The preparation process comprises the following steps: : adding polycarbonate, a toughening agent, a lubricant, an antioxidant and a flame retardant into a high-speed stirrer in proportion, uniformly mixing, adding the mixture into a double-screw extruder from a main feed, adding the glass fiber treated by a coupling agent from a side material, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the high-impact-resistance and high-flame-retardant glass fiber reinforced polycarbonate composite material, wherein the processing temperature is 250-280 ℃, the rotating speed is 220-260r/min, and the main feed frequency is 18-25 Hz.
9. The invention has the beneficial effects that:
(1) the polycarbonate composite material prepared by the invention has excellent mechanical property, dimensional stability, weather resistance, excellent impact resistance and good flame retardant property, compared with the traditional material, the flame retardant property is better, the rigidity and the toughness are more balanced, and the problems of poor impact resistance and low flame retardant capability of glass fiber reinforced polycarbonate are solved, (2) the preparation process is simple, the cost is lower, and the large-scale industrial production is easy to carry out.
Detailed Description
The high-impact-resistance flame-retardant reinforced polycarbonate composite material comprises the following components in parts by weight:
72.8-88.9 parts of polycarbonate
10-20 parts of glass fiber filler
Coupling agent: 0.3 to 0.8 portion
A toughening agent: 3.0 to 7.0 parts
Flame retardant: 0.2 to 1.0 portion
Antioxidant: 0.4 to 1.0 portion
Lubricant: 0.2 to 1.0 portion.
1. Preferably, the polycarbonate consists of at least one polycarbonate. The melt index of the polycarbonate is 10-30g/10min (300 ℃, 1.2 Kg).
2. Preferably, the glass fiber filler is at least one of alkali glass fiber, alkali-free glass fiber, high-strength glass fiber and chemical-resistant glass fiber. Further preferred is chopped glass fiber (ECS 307) of chongqing international composite material co.
3. Preferably, the coupling agent is composed of at least one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent. Further preferably a silane coupling agent (KH 550).
4. Preferably, the toughening agent is composed of at least one of methyl acrylate-butadiene-styrene copolymer (MBS), ethylene-methyl acrylate copolymer (EMA) and styrene-maleic anhydride copolymer (SMA), and more preferably EMA (1125 AC) from DuPont, USA.
5. Preferably, the flame retardant is composed of at least one of an organic phosphorus-based flame retardant, a silicon-based flame retardant, a sulfonate-based flame retardant and PTFE, and more preferably a sulfonate-based flame retardant SW-202 manufactured by Sanweisha chemical Co., Ltd, Dongguan.
6. Preferably, the lubricant is one or more of polyethylene wax, polycarbonate wax, calcium stearate, EBS, and TAF.
7. Preferably, the antioxidant is prepared by compounding hindered phenol antioxidant and phosphite antioxidant according to the proportion of 1: 1. Further preferred are 1010 and 168 by basf.
8. Preferably, the preparation process comprises: : adding polycarbonate, a toughening agent, a lubricant, an antioxidant and a flame retardant into a high-speed stirrer in proportion, uniformly mixing, adding the mixture into a double-screw extruder from a main feed, adding the glass fiber treated by a coupling agent from a side material, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the high-impact-resistance and high-flame-retardant glass fiber reinforced polycarbonate composite material, wherein the processing temperature is 250-280 ℃, the rotating speed is 220-260r/min, and the main feed frequency is 18-25 Hz.
The invention is further illustrated by the following specific examples,
the formulation compositions of the examples and comparative examples are shown in Table 1
TABLE 1 formulation composition (in mass%) of examples and comparative examples
| Raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Polycarbonate resin | 83.1 | 78.1 | 72.8 | 84.7 | 79.7 | 88.9 |
| Glass fiber | 10 | 15 | 20 | 10 | 10 | 10 |
| Coupling agent | 0.5 | 0.5 | 0.5 | 0.3 | 0.8 | 0.5 |
| Toughening agent | 5.0 | 5.0 | 5.0 | 3.0 | 7.0 | 0 |
| Flame retardant | 0.5 | 0.5 | 0.5 | 0.2 | 1.0 | 0 |
| Antioxidant agent | 0.4 | 0.4 | 0.4 | 0.8 | 1.0 | 0.4 |
| Lubricant agent | 0.5 | 0.5 | 0.8 | 1.0 | 0.5 | 0.2 |
The lubricant used in table 1 is IAF, the glass fiber is alkali-free chopped glass fiber, the diameter is 13 μm, the length is 3mm, and the flame retardant is sulfonate flame retardant SW-202 and anti-dripping agent PTFE with the ratio of 1:1, the proportion of the used antioxidant 1010 to 168 is 1: 1.
Weighing the raw materials according to the proportion, adding the raw materials into a high-speed stirrer, uniformly mixing, adding the raw materials into a double-screw extruder from a main feed, adding glass fibers from a side feed, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the polycarbonate composite material with high flame retardance, high impact resistance and high strength, wherein the processing temperature is 250-280 ℃.
The composite materials obtained after processing were tested by the test standards shown in table 2, and table 3 shows the test results of the corresponding examples and comparative examples.
| Detecting items | Unit of | Test standard |
| Tensile strength | MPa | ISO527-2 |
| Bending strength | MPa | ISO 178 |
| Flexural modulus | MPa | ISO 178 |
| Fuse finger | g/10min | ISO 1133 |
| Unnotched impact strength of simply supported beam | KJ/m2 | ISO 179 |
| Impact strength of simply supported beam gap | KJ/m2 | ISO 179 |
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Tensile strength | 72.5 | 82.8 | 92.3 | 78.5 | 68.5 | 79.5 |
| Bending strength | 115.4 | 135.9 | 152.3 | 123.5 | 96.5 | 123.4 |
| Flexural modulus | 3900 | 4513 | 5500 | 4010 | 3650 | 4210 |
| Fuse finger | 8.9 | 7.5 | 10.2 | 9.3 | 7.6 | 10.5 |
| Unnotched impact strength of simply supported beam | 95.8 | 73.5 | 65.5 | 86.5 | 99.3 | 67.7 |
| Impact strength of simply supported beam notch | 15.8 | 11.9 | 7.6 | 13.4 | 17.8 | 8.2 |
| Flame retardant rating of U L94 | V-0 | V-0 | V-0 | V-1 | V-0 | V-2 |
It can be seen from table 3 that, as the content of the toughening agent increases, the impact resistance of the system material gradually increases, but the addition amount exceeds 5 parts, the impact resistance of the composite material is not significantly increased, because the EMA type elastomer toughening agent contains vinyl capable of absorbing impact energy, which is dispersed in a polycarbonate matrix in a spherical shape, when the material is impacted, the EMA type elastomer toughening agent serves as a stress concentrator to generate deformation to absorb energy, and simultaneously, silver streaks and shear bands are formed, and on the other hand, the expansion of the silver streaks into cracks is limited, so that as the content of the EMA increases, particles serving as the stress concentrator gradually increases, the absorbed impact energy is more and more, the impact strength of the whole system is increased, but when the content of the EMA type elastomer exceeds 5 parts, the elastomer of the matrix exceeds the saturation degree of the matrix toughening agent, and the impact strength of the material is not increased; compared with the comparative example 1, the impact strength and the flame retardant performance of the examples 1-5 are improved to a certain extent, and when the flame retardant is 0.5 part, the flame retardant grade of the system material can reach V-0.
It should be understood by those skilled in the art that various changes and modifications can be made to the above embodiments without departing from the scope of the present invention, and any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention are within the scope of the present invention.
Claims (9)
1. A high-impact-resistance flame-retardant reinforced polycarbonate composite material is characterized in that: the composite material is prepared from the following raw materials in parts by weight:
72.8-88.9 parts of polycarbonate
10-20 parts of glass fiber filler
Coupling agent: 0.3 to 0.8 portion
A toughening agent: 3.0 to 7.0 parts
Flame retardant: 0.2 to 1.0 portion
Antioxidant: 0.4 to 1.0 portion
Lubricant: 0.2 to 1.0 portion.
2. The high impact resistant flame retardant reinforced polycarbonate composite material as claimed in claim 1, wherein: the melt index of the polycarbonate is 10-30g/10min (300 ℃, 1.2 Kg).
3. The high impact flame retardant reinforced polycarbonate composite material of claim 1, wherein: the glass fiber filler is at least one of alkali glass fiber, alkali-free glass fiber, high-strength glass fiber and chemical-resistant glass fiber.
4. The high impact flame retardant reinforced polycarbonate composite material of claim 1, wherein: the coupling agent is composed of at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent.
5. The high impact flame retardant reinforced polycarbonate composite material of claim 1, wherein: the toughening agent is composed of at least one of methyl acrylate-butadiene-styrene copolymer (MBS), ethylene-methyl acrylate copolymer (EMA) and styrene-maleic anhydride copolymer (SMA).
6. The high impact flame retardant reinforced polycarbonate composite material of claim 1, wherein: the flame retardant is composed of at least one of organic phosphorus, silicon, sulfonate and PTFE.
7. The high impact flame retardant reinforced polycarbonate composite material of claim 1, wherein: the antioxidant is prepared by compounding hindered phenol antioxidant and phosphite antioxidant according to the proportion of 1: 1.
8. The high impact flame retardant reinforced polycarbonate composite material of claim 1, wherein: the lubricant is one or more of polyethylene wax, polycarbonate wax, calcium stearate, EBS and TAF.
9. The high impact flame retardant reinforced polycarbonate composite material according to any one of claims 1 to 8, characterized by comprising the following preparation processes: adding polycarbonate, a toughening agent, a lubricant, an antioxidant and a flame retardant into a high-speed stirrer in proportion, uniformly mixing, adding the mixture into a double-screw extruder from a main feed, adding the glass fiber treated by a coupling agent from a side material, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the high-impact-resistance and high-flame-retardant glass fiber reinforced polycarbonate composite material, wherein the processing temperature is 250-280 ℃, the rotating speed is 220-260r/min, and the main feed frequency is 18-25 Hz.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112341779A (en) * | 2020-10-21 | 2021-02-09 | 工业和信息化部电子第五研究所华东分所 | High CTI halogen-free flame-retardant reinforced polycarbonate and preparation method and application thereof |
| CN112538250A (en) * | 2020-12-02 | 2021-03-23 | 赵光明 | Antioxidant plastic formula |
| CN115124826A (en) * | 2022-08-02 | 2022-09-30 | 上海中镭新材料科技有限公司 | Glass fiber reinforced polycarbonate material and preparation method and application thereof |
| CN115160757A (en) * | 2022-07-01 | 2022-10-11 | 中国石油化工股份有限公司 | Flame-retardant glass fiber reinforced PC material and preparation method thereof |
| CN115286915A (en) * | 2022-08-31 | 2022-11-04 | 河南德利新能源材料有限公司 | Preparation method of polycarbonate composition |
| CN115651385A (en) * | 2022-10-31 | 2023-01-31 | 金发科技股份有限公司 | Polycarbonate composite material with stable shrinkage rate and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115651385A (en) * | 2022-10-31 | 2023-01-31 | 金发科技股份有限公司 | Polycarbonate composite material with stable shrinkage rate and preparation method and application thereof |
| CN115651385B (en) * | 2022-10-31 | 2023-09-26 | 金发科技股份有限公司 | Polycarbonate composite material with stable shrinkage rate and preparation method and application thereof |
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