CN106995602B - A kind of high-modulus height flowing halogen-free flame retardant PC/ABS alloy material and preparation method thereof - Google Patents
A kind of high-modulus height flowing halogen-free flame retardant PC/ABS alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of PC/ABS alloy materials, including the component calculated in parts by mass as follows: 30-50 parts of PC resin；8-20 parts of ABS resin；15-25 parts of carbon fiber；10-15 parts of poly aromatic ester phosphate flame retardants；Silicon systems triazine is at 0.1-5 parts of charcoal synergist；Ultra-fine phosphate 0.5-3 parts；1-5 parts of toughener；0.5-1 parts of antioxidant；0.5-1 parts of lubricant；Wherein, the ultra-fine phosphate partial size is 10-50 μm, and the carbon fiber length is 2-5mm.The PC/ABS alloy material has high-modulus and high fluidity, and has both excellent flame retardant property and mechanical property simultaneously, can be applied to the ultra-thin product of electronic apparatus, auto industry and space industry, industrialization prospect is wide, there is very high economic value.
Description
Technical field
The invention belongs to technical field of polymer materials, in particular it relates to a kind of flowing Halogen resistance of high-modulus height
Fire PC/ABS alloy material and preparation method thereof.
Background technique
PC/ABS alloy is the engineering thermoplastic of a kind of function admirable, handling ease, quality-high and inexpensive, great commercialization value
Plastic alloy is widely used in the fields such as auto industry, household electrical appliance and office equipment.Prevent to meet in application field
Fire safety requirement, PC/ABS alloy must be then on this basis with good anti-flammability, fire retardation PC/ABS alloy material
The anti-flammability for promoting material, has good fire protecting performance.About PC/ABS alloy studies have shown that brominated flame-retardant to material
Flame retardant effect it is best, the fire-retardant mechanism of action is to inhibit gas phase process, but their addition will be greatly reduced material
Mechanical property, the deficiencies of sharply increasing additionally there are smoke when burning, corrode process equipment, high poison decomposition product is precipitated.
To overcome influence of the fire retardant to PC/ABS alloy material mechanical property, people enhance it using carbon fiber
It is modified.In recent years, automobile, electronic apparatus and aerospace industry flourish, and have driven fibre reinforced PC/ABS alloy and correlation
The fast development of industry.Alloy demand kept average annual 8% to be incremented by recent years, it is contemplated that will to 2017 China PC/ABS alloy demands
Reach 3.6 ten thousand tons.However, the addition of carbon fiber can generate " candle wick effect ", the flame retardant property of material is bad.The carbon fiber in China
Enhance the development of PC alloy technology and be in the starting stage, lag far behind developed country, there are bottleneck, existing carbon fibers for many aspects
Enhancing PC/ABS alloy is unable to satisfy the demand of technical grade and military field.
Summary of the invention
Based on this, the invention reside in overcoming the deficiencies of existing technologies, a kind of novel fibre reinforced PC/ABS conjunction is provided
Golden material, the PC/ABS alloy material has high-modulus and high fluidity, and has both excellent flame retardant property and mechanics simultaneously
Performance can be applied to the ultra-thin product of electronic apparatus, auto industry and space industry, and industrialization prospect is wide, there is very high economy
Value.
Its technical solution is as follows:
A kind of PC/ABS alloy material, including the component calculated in parts by mass as follows:
30-50 parts of PC resin；
8-15 parts of ABS resin；
25-35 parts of carbon fiber；
1-8 parts of poly aromatic ester phosphate flame retardants；
Silicon systems triazine is at 0.1-3 parts of charcoal synergist；
Ultra-fine phosphate 0.5-3 parts；
1-5 parts of toughener；
0.5-1 parts of antioxidant；
0.5-1 parts of lubricant；
Wherein, the ultra-fine phosphate partial size is 10-50 μm, and the carbon fiber length is 2-5mm.
The present invention is by compounding poly aromatic ester phosphate flame retardants, silicon systems triazine at charcoal synergist, ultra-fine phosphate etc.
Solve carbon fiber bring " candle wick effect ", so that PC/ABS alloy material has excellent flame retardant property, while the present invention
PC/ABS alloy material maintain carbon fiber network distribution, so that the mechanics for greatly improving PC/ABS alloy material is strong
Degree.Poly aromatic ester phosphate flame retardants, silicon systems triazine improve collaboration and imitate at charcoal at the collocation of charcoal synergist in the present invention
Fruit, thus further very high flame retardant effect；Ultra-fine phosphatic addition can cooperate with the mobility for improving melt, improve carbon
In the dispersion effect for entering inside screw the rigidity and modulus of PC/ABS alloy material greatly improved, in low-gravity item in fiber
Under part, accomplish the modulus of superelevation.
The poly aromatic ester phosphate flame retardants are oligomeric aryl phosphate ester, phosphorus content in one of the embodiments,
≥10%.Specifically, the oligomeric aryl phosphate ester is PX-220.
The silicon systems triazine is triazines macromolecular carbon forming synergist at charcoal synergist in one of the embodiments, is contained
Nitrogen quantity >=40%.Specifically, the silicon systems triazine is CFA at charcoal synergist.
The ultra-fine phosphate is ultra-fine basic zirconium phosphate in one of the embodiments,.
The ultra-fine basic zirconium phosphate partial size is 30 μm in one of the embodiments,.
The carbon fiber is chopped carbon fiber, length 4mm, monofilament 12K in one of the embodiments,.
The PC resin melt index is 10-20g/10min in one of the embodiments,.
The preparation method of the PC/ABS alloy material, comprising the following steps:
S1, each raw material is weighed by the formula of the PC/ABS alloy material；
S2, PC and ABS resin are dried at a temperature of 90 DEG C the small inch of 3-4, is then uniformly mixed with other raw materials；
S3, the raw material mixed is placed in the lower hopper of extruder, through double screw extruder melting extrusion be granulated to get
PC/ABS alloy material.
The step S3 in one of the embodiments, are as follows: the raw material mixed is placed in the lower hopper of extruder, is passed through
Double screw extruder melting extrusion is granulated, technological parameter are as follows: 210-220 DEG C of area's temperature, two 255-260 DEG C of area's temperature, 3rd area
250-255 DEG C of temperature, four 245-250 DEG C of area's temperature, five 240-245 DEG C of area's temperature, six 235-240 DEG C of area's temperature, seven area's temperature
230-235 DEG C, eight 225-230 DEG C of area's temperature, nine 225-230 DEG C of area's temperature, 240-245 DEG C of die head temperature, the revolving speed of host is
240-260r/min, the revolving speed of feeding are 60-70r/min, and the revolving speed of side feed material is 30-35r/min, obtains PC/ABS alloy material
Material.
The beneficial effects of the present invention are:
(1) collocation of the present invention oligomeric aryl phosphate ester fire retardant, silicon systems triazine carbon forming agent, improves PC/ABS alloy material
The collaboration of material further improves flame retarding efficiency at charcoal effect；
(2) ultra-fine phosphatic addition can cooperate with the mobility for improving melt, further ensure carbon fiber and entering
The dispersion effect of inside screw, to greatly improve rigidity and modulus；
(3) present invention solves carbon fiber bring " candle wick effect " in PC/ABS alloy material, improves halogen-free flameproof
The flame retardant property of agent, while carbon fiber network distribution is remain, mechanical strength is greatly improved, under the conditions of low-gravity, is done
To the modulus of superelevation, PC/ABS of the invention has both excellent flame retardant property and mechanical property, it is ultra-thin to can be applied to electronic apparatus
Product, auto industry and space industry, industrialization prospect is wide, there is very high economic value.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, below in conjunction with specific embodiment, to this
Invention is described in further detail.It should be understood that the specific embodiments described herein are only to explain this hair
It is bright, and the scope of protection of the present invention is not limited.
Raw material used in following embodiment is as follows:
Oligomeric aryl phosphate ester fire retardant PX-220: production, phosphorus content >=10% are contained in Zhejiang ten thousand；
Oligomeric aryl phosphate ester fire retardant PX-200: big eight chemistry of Japan；
Silicon systems triazine is at charcoal synergist CFA: liking the macro molecular triazine carbon forming agent of good Chemical Manufacture, nitrogen content >=40%；
Silicon systems triazine is at charcoal synergist CTJ-1: Pu Saifu phosphorus chemistry Co., Ltd of Qingyuan City；
Ultra-fine basic zirconium phosphate: day Yao's industry production, 30 μm of partial size, phosphorus pentoxide content >=30%；
Ultra-fine hypo-aluminum orthophosphate: Zhong Shan Kang Nuode company, 10 μm of partial size；
Toughener: Japanese clock deep pool acrylic resin M511, white powder；
Carbon fiber A: toray chopped carbon fiber, length 4mm, monofilament 12K；
Carbon fiber B: Japanese MT S company, length 3mm, monofilament 10K；
PC resin: Japan goes out light IR2200, melt index 10g/10min；
PC resin: South Korea Hunan petrochemical industry PC1100, melt index 11g/10min；
ABS resin: CNOOC H181,40 g/10min of melt index；
ABS resin: Tianjin Dagu DG417,17 g/10min of melt index；
Antioxidant: antioxidant 1010, it is common commercially available；
Lubricant: PETS, it is common commercially available.
Embodiment 1
A kind of PC/ABS alloy material is formulated as follows: 50 parts of PC resin IR2200,13 parts of ABS resin H181, and oligomeric virtue
12 parts of base phosphate flame retardant PX-220, silicon systems triazine is at 4 parts of charcoal synergist CFA, 2 parts of ultra-fine basic zirconium phosphate, toughener 3
Part, 15 parts of carbon fiber A, 0.5 part of antioxidant, 0.5 part of lubricant.
The present embodiment PC/ABS alloy material the preparation method is as follows:
S1, each raw material is weighed by the formula of the PC/ABS alloy material；
S2, PC and ABS resin are dried at a temperature of 90 DEG C the small inch of 3-4, is then uniformly mixed with other raw materials；
S3, the raw material mixed is placed in the lower hopper of extruder, is granulated through double screw extruder melting extrusion, technique
Parameter are as follows: 210-220 DEG C of area's temperature, two 255-260 DEG C of area's temperature, three 250-255 DEG C of area's temperature, four area temperature 245-250
DEG C, five 240-245 DEG C of area's temperature, six 235-240 DEG C of area's temperature, seven 230-235 DEG C of area's temperature, eight 225-230 DEG C of area's temperature, nine
225-230 DEG C of area's temperature, 240-245 DEG C of die head temperature, the revolving speed of host is 240-260r/min, and the revolving speed of feeding is 60-
The revolving speed of 70r/min, side feed material are 30-35r/min, obtain PC/ABS alloy material.
Embodiment 2
A kind of PC/ABS alloy material is formulated as follows: 45 parts of PC resin IR2200,15 parts of ABS resin H181, and oligomeric virtue
13 parts of base phosphate flame retardant PX-220, silicon systems triazine is at 5 parts of charcoal synergist CFA, 2 parts of ultra-fine basic zirconium phosphate, toughener 4
Part, 15 parts of carbon fiber A, 0.5 part of antioxidant, 0.5 part of lubricant.
The preparation method of PC/ABS alloy material is same as Example 1 in the present embodiment.
Embodiment 3
A kind of PC/ABS alloy material is formulated as follows: 50 parts of PC resin IR2200,8 parts of ABS resin H181, and oligomeric virtue
10 parts of base phosphate flame retardant PX-220, silicon systems triazine is at 1 part of charcoal synergist CFA, 2 parts of ultra-fine basic zirconium phosphate, toughener 3
Part, 25 parts of carbon fiber A, 0.5 part of antioxidant, 0.5 part of lubricant.
The preparation method of PC/ABS alloy material is same as Example 1 in the present embodiment.
Embodiment 4
A kind of PC/ABS alloy material is formulated as follows: 45 parts of PC resin IR2200,15 parts of ABS resin H181, and oligomeric virtue
15 parts of base phosphate flame retardant PX-220, silicon systems triazine is at 3 parts of charcoal synergist CFA, 1 part of ultra-fine basic zirconium phosphate, toughener 3
Part, 20 parts of carbon fiber A, 0.5 part of antioxidant, 0.5 part of lubricant.
The preparation method of PC/ABS alloy material is same as Example 1 in the present embodiment.
Embodiment 5
A kind of PC/ABS alloy material is formulated as follows: 30 parts of PC resin PC1100,20 parts of ABS resin DG417, oligomeric
14 parts of aryl phosphate ester fire retardant PX-220, silicon systems triazine is at 3 parts of charcoal synergist CFA, 3 parts of ultra-fine basic zirconium phosphate, toughener 5
Part, 24 parts of carbon fiber A, 0.5 part of antioxidant, 0.5 part of lubricant.
The preparation method of PC/ABS alloy material is same as Example 1 in the present embodiment.
Embodiment 6
A kind of PC/ABS alloy material is formulated as follows: 50 parts of PC resin IR2200,13 parts of ABS resin H181, and oligomeric virtue
12 parts of base phosphate flame retardant PX-200, silicon systems triazine is at 4 parts of charcoal synergist CTJ-1,2 parts of ultra-fine basic zirconium phosphate, toughener 3
Part, 15 parts of carbon fiber A, 0.5 part of antioxidant, 0.5 part of lubricant.
The preparation method of PC/ABS alloy material is same as Example 1 in the present embodiment.
Embodiment 7
A kind of PC/ABS alloy material is formulated as follows: 50 parts of PC resin IR2200,13 parts of ABS resin H181, and oligomeric virtue
12 parts of base phosphate flame retardant PX-220, silicon systems triazine is at 4 parts of charcoal synergist CFA, 2 parts of ultra-fine hypo-aluminum orthophosphate, toughener 3
Part, 15 parts of carbon fiber B, 0.5 part of antioxidant, 0.5 part of lubricant.
The preparation method of PC/ABS alloy material is same as Example 1 in the present embodiment.
Comparative example 1
A kind of PC/ABS alloy material is formulated as follows: 50 parts of PC resin IR2200,13 parts of ABS resin H181, and polyphosphoric acid
12 parts of amine fire retardant, silicon systems triazine is at 4 parts of charcoal synergist CFA, 2 parts of ultra-fine basic zirconium phosphate, and 3 parts of toughener, carbon fiber A 15
Part, 0.5 part of antioxidant, 0.5 part of lubricant.
The preparation method of PC/ABS alloy material is same as Example 1 in this comparative example.
Comparative example 2
A kind of PC/ABS alloy material, be formulated as follows: 50 parts of PC resin IR2200,13 parts of ABS H181 resin is oligomeric
12 parts of aryl phosphate ester fire retardant PX-220, at 4 parts of charcoal synergist CTJ-1,2 parts of ultra-fine basic zirconium phosphate, 3 parts of toughener, carbon
15 parts of fiber A, 0.5 part of antioxidant, 0.5 part of lubricant.
The preparation method of PC/ABS alloy material is same as Example 1 in this comparative example.
Comparative example 3
A kind of PC/ABS alloy material is formulated as follows: 50 parts of PC resin, 13 parts of ABS resin, and oligomeric aryl phosphate ester resistance
12 parts of agent PX-220 of combustion, silicon systems triazine is at 4 parts of charcoal synergist CFA, and (Xiamen prosperous Da Kang inorganic material Co., Ltd is raw for basic zirconium phosphate
Produce) 2 parts, 3 parts of toughener, 15 parts of carbon fiber A, 0.5 part of antioxidant, 0.5 part of lubricant.
The preparation method of PC/ABS alloy material is same as Example 1 in this comparative example.
Further performance detection is made to halogen-free flameproof enhancing PC/ABS prepared by above-described embodiment and comparative example below.
Standard surveys material mechanical performance as follows:
The resin that Examples 1 to 8 and comparative example 1~3 have been granulated is placed in air dry oven at a temperature of 90 °C dry
2-3 hours, the sample preparation on 80T injection molding machine.Cooling placement is tested after 24 hours.Testing standard is Unite States Standard, and test temperature is
Room temperature, specific as follows:
(1) tensile strength standard: ASTM D638, batten are stretched having a size of 57mm × 127mm × 3.2mm (effective dimensions)
Speed is 50mm/min；
(2) bending strength standard: ASTM D790, batten is having a size of 127mm × 13mm × 3.2mm, rate of bending 2mm/
min；
(3) Chalpy impact standard: ASTM D256, for batten having a size of 64mm × 12.7mm × 3.2mm, notch is remaining wide
Degree is 10.12mm；
(4) melt index standard: ASTM D1238, test condition are 230 °C/3.8kg；
(5) it flame retardant property: is tested according to 94 standard of UL；
(6) it glowing filament performance: is tested according to IEC60695 standard.
1 embodiment PC/ABS alloy material performance of table
2 comparative example PC/ABS alloy material of table and commercially available PC alloy property
By the test data in table 1 it is found that PC/ABS alloy material prepared by the present invention has excellent mechanical property,
Notch impact strength is not less than 130J/m, flame retardant rating V-0, and tensile strength is not less than 100Mpa, and bending strength is not less than
135Mpa, bending modulus may be up to 9600Mpa, be significantly better than other PC/ABS alloy materials.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (5)
1. a kind of PC/ABS alloy material, which is characterized in that including the component calculated in parts by mass as follows:
30-50 parts of PC resin；
8-20 parts of ABS resin；
15-25 parts of carbon fiber；
10-15 parts of poly aromatic ester phosphate flame retardants；
Silicon systems triazine is at 0.1-5 parts of charcoal synergist；
Ultra-fine phosphate 0.5-3 parts；
1-5 parts of toughener；
0.5-1 parts of antioxidant；
0.5-1 parts of lubricant；
Wherein, the ultra-fine phosphate partial size is 10-50 μm, and the carbon fiber length is 2-5mm；
The poly aromatic ester phosphate flame retardants are oligomeric aryl phosphate ester fire retardant PX-220 or the day that production is contained in Zhejiang ten thousand
The oligomeric aryl phosphate ester fire retardant PX-200 of this big eight chemical production；
The silicon systems triazine is to like the macro molecular triazine of good Chemical Manufacture into charcoal synergist CFA at charcoal synergist；
The ultra-fine phosphate is the grain of ultra-fine basic zirconium phosphate or Zhong Shan Kang Nuode company that day partial size of Yao's industry production is 30 μm
The ultra-fine hypo-aluminum orthophosphate that diameter is 10 μm.
2. PC/ABS alloy material according to claim 1, which is characterized in that the carbon fiber is chopped carbon fiber, length
4mm, monofilament 12K.
3. PC/ABS alloy material according to claim 1, which is characterized in that the PC resin melt index is 10-20g/
10min。
4. the preparation method of PC/ABS alloy material described in claim 1-3 any claim, which is characterized in that including following
Step:
S1, each raw material is weighed by the formula of PC/ABS alloy material described in claim 1-3 any claim；
S2, PC and ABS resin are dried at a temperature of 90 DEG C the small inch of 3-4, is then uniformly mixed with other raw materials；
S3, the raw material mixed is placed in the lower hopper of extruder, is granulated through double screw extruder melting extrusion to get PC/
ABS alloy material.
5. preparation method according to claim 4, which is characterized in that the step S3 are as follows: be placed in the raw material mixed crowded
It out in the lower hopper of machine, is granulated through double screw extruder melting extrusion, technological parameter are as follows: 210-220 DEG C of area's temperature, two area's temperature
255-260 DEG C of degree, three 250-255 DEG C of area's temperature, four 245-250 DEG C of area's temperature, five 240-245 DEG C of area's temperature, six area's temperature
235-240 DEG C, seven 230-235 DEG C of area's temperature, eight 225-230 DEG C of area's temperature, nine 225-230 DEG C of area's temperature, die head temperature 240-
245 DEG C, the revolving speed of host is 240-260r/min, and the revolving speed of feeding is 60-70r/min, and the revolving speed of side feed material is 30-35r/
Min obtains PC/ABS alloy material.
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| CN107474510B (en) * | 2017-08-29 | 2019-11-15 | 华南理工大学 | High fluidity and high rigidity halogen-free flame retardant PC/ABS mixture and preparation method thereof |
| CN109423023B (en) * | 2017-09-01 | 2021-01-05 | 汉达精密电子(昆山)有限公司 | Halogen-free flame-retardant PC antistatic material and product thereof |
| CN109867904B (en) * | 2017-12-05 | 2021-05-28 | 广州金发碳纤维新材料发展有限公司 | Carbon fiber reinforced ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN108624027B (en) * | 2018-05-30 | 2020-02-18 | 华南理工大学 | A kind of catalytic carbon-forming high-efficiency halogen-free flame-retardant PC/ABS mixture and preparation method thereof |
| CN111560162A (en) * | 2020-07-06 | 2020-08-21 | 华北电力大学 | Preparation method of enhanced PC/ABS alloy flame-retardant plate |
| CN114591616A (en) * | 2022-02-25 | 2022-06-07 | 金发科技股份有限公司 | Flame-retardant polycarbonate composition and preparation method and application thereof |
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