CN103044885A - Halogen-free flame-retardant low-temperature resistant polycarbonate and preparation method thereof - Google Patents
Halogen-free flame-retardant low-temperature resistant polycarbonate and preparation method thereof Download PDFInfo
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- CN103044885A CN103044885A CN2012105598968A CN201210559896A CN103044885A CN 103044885 A CN103044885 A CN 103044885A CN 2012105598968 A CN2012105598968 A CN 2012105598968A CN 201210559896 A CN201210559896 A CN 201210559896A CN 103044885 A CN103044885 A CN 103044885A
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Abstract
The invention relates to the technical field of modification of thermoplastic polymer materials, and discloses a halogen-free flame-retardant low-temperature resistant polycarbonate applied to household appliances, automotive electronics and the like. The polycarbonate is prepared from the following materials: polycarbonate, an acrylate flexibilizer, a flame retardant, an antioxidant and a processing aid. The invention further discloses a method for preparing the halogen-free flame-retardant low-temperature resistant polycarbonate. The invention aims to provide an ultralow-temperature (40 DEG C below zero) resistant halogen-free flame-retardant excellent engineering plastic polycarbonate, which can be applied to a requirement-critical occasion, such as the periphery of a washer pump and an automotive ignition system.
Description
Technical field
The present invention relates to the preparation method of the low temperature resistant polycarbonate of a kind of halogen-free flameproof, belong to thermoplastic macromolecule material modification technology field.Product of the present invention is anti-very low temperature (40 ℃) and the excellent engineering plastics polycarbonate that possesses halogen-free flameproof, can be applied to require harsh occasion such as washing machine pump machine periphery, automotive ignition system etc.
Background technology
Polycarbonate (be called for short PC) is the high molecular polymer that contains carbonate group in the molecular chain, can be divided into the broad varietys such as aliphatics, aromatic series, fat-aromatic series according to the structure of ester group.Wherein most widely used is aromatic series, has good mechanical property and optical property, is widely used in the fields such as automobile making, electronic apparatus, optics, aerospace; Its outstanding advantage has the transparency height, intensity is high, shock-resistance is excellent, creep properties is little, and good thermotolerance, dimensional precision are high.But because aromatic series PC molecular chain rigidity is large, produce easily stress cracking; Because it has higher second-order transition temperature (TG), so mechanical property at low temperatures is relatively poor; Though PC has certain flame retardant resistance (oxygen index is 26), can't satisfy harsh environment for use, so need carry out it flame-retardant modified, to prepare fire-retardant low temperature resistant excellent engineering plastics.
PC is carried out the low-temperature flexibility modification, be base mateiral such as CN1388178 with polycarbonate and polyolefin elastomer, add again the polyolefin elastomer graft copolymer and the ionic polymer expanding material carries out modification, although can improve the low temperature brittleness of PC, improved amplitude is limited, and (30 ℃ of notched Izod impact strength are 46.4Kj.m
-2), and the mechanical properties decrease of material is severe, and tensile strength only is 43.3MPa, and fall is 25.5%.
Summary of the invention
Purpose of the present invention can be applied to require harsh occasion such as washing machine pump machine periphery, automotive ignition system etc. at the excellent engineering plastics polycarbonate that a kind of anti-very low temperature (40 ℃) and halogen-free flameproof are provided.
Another object of the present invention provides the preparation method of the low temperature resistant polycarbonate of a kind of halogen-free flameproof.
In order to realize above-mentioned the first goal of the invention, technical scheme of the present invention is:
The low temperature resistant polycarbonate of a kind of halogen-free flameproof is comprised of following material: polycarbonate, esters of acrylic acid toughner, halogen-free flame retardants, oxidation inhibitor, processing aid.
Alternatively, the low temperature resistant polycarbonate of described halogen-free flameproof is made by following material by weight percentage:
Polycarbonate 88～95%;
Esters of acrylic acid toughner 4～8%;
Halogen-free flame retardants 0.07～0.1%;
Oxidation inhibitor 0.3～1%;
Processing aid 0.6～0.9%;
The present invention adopts esters of acrylic acid rubber, because containing the vinylbenzene section of rigidity in its structure, so less on the mechanical property impact of PC; The low Tg of the acrylic rubber in the molecular structure can guarantee that the PC of modification has good low-temperature flexibility, and good with the molecular chain consistency of PC, has mechanical property and low temperature properties under the normal temperature concurrently.This kind modification PC except possess with the basically identical mechanical property and thermal characteristics of pure PC, also possess fire-retardant good, low temperature resistant (40 ℃) outstanding characteristics.
Alternatively, the molecular weight of described polycarbonate is 20000～40000 bisphenol A polycarbonate, selects the PC of this molecular weight mobile better with balance of mechanical properties.
Alternatively, the described esters of acrylic acid toughner multipolymer that is Acrylate-styrene bipolymer-acrylic rubber.Because its second-order transition temperature (TG) is lower than-50 degree, and good with the consistency of PC, the low temperature that can better be applied to PC is toughness reinforcing.
Alternatively, described halogen-free flame retardants is aromatic sulphonate, because it is reactive flame retardant, and energy and PC complete reaction, and addition is little, does not affect mechanical property;
Alternatively, described oxidation inhibitor is β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
Alternatively, described processing aid is that lubricant pentaerythritol stearate and viscosity are the methyl-silicone oil of 1000CPS.
The preparation method of the low temperature resistant polycarbonate of a kind of halogen-free flameproof may further comprise the steps:
S1. drying treatment polycarbonate, halogen-free flame retardants, toughner, oxidation inhibitor, processing aid, wherein,
The temperature of dry polycarbonate is 100 ~ 120 ℃, and be 4 ~ 8 hours time of drying;
Dry halogen-free flame retardants, toughner, oxidation inhibitor, processing aid temperature are 65 ~ 85 ℃, and be 3 ~ 6 hours time of drying;
S2. take by weighing each component according to following weight percent:
Polycarbonate 88～95%;
Esters of acrylic acid toughner 4～8%;
Halogen-free flame retardants 0.07～0.1%;
Oxidation inhibitor 0.3～1%;
Processing aid 0.6～0.9%.
All raw materials that S3. will take by weighing mix;
S4. mixing raw material is added parallel double-screw extruder, through melt extruding granulation.
Alternatively, described step S3 specifically: all raw material stirring that will take by weighing at normal temperatures 10～20 minutes mix.
Preferably, the processing condition of melt stage are among the described step S4:
The screw diameter of described parallel double-screw extruder is 35～75 millimeters, and screw slenderness ratio is 36:1;
In dual-screw-stem machine temperature control section, district's temperature is 220 ℃, and two district's temperature are 240 ℃, and three district's temperature are 255 ℃, four district's temperature are 270 ℃, and five district's temperature are 280 ℃, and six district's temperature are 280 ℃, seven district's temperature are 270 ℃, and eight district's temperature are 270 ℃, and the head temperature of dual-screw-stem machine is 275 ℃;
Screw speed is 250～450r/min, and too little rotating speed output is not high; Rotating speed is too large, and PC easily forms excessive internal stress; So select the rotating speed of 250～450r/min more suitable;
Compared with prior art, use technical scheme of the present invention, following beneficial effect arranged:
The low temperature resistant polycarbonate of halogen-free flameproof of the present invention by in prescription, add polycarbonate, halogen-free flame retardants, an amount of esters of acrylic acid toughner, oxidation inhibitor, processing aid forms, improve the flame retardant properties of PC and do not reduce its mechanical property by the halogen-free flame retardants that adds response type, add simultaneously the multipolymer of Acrylate-styrene bipolymer-acrylic rubber, the low-temperature flexibility of energy Effective Raise PC can possess use properties at low temperatures.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
The embodiment of the low temperature resistant polycarbonate of a kind of halogen-free flameproof of the present invention, be comprised of following material: polycarbonate, acrylate toughner, oxidation inhibitor, halogen-free flame retardants and processing aid form, by adding the low temperature toughner of halogen-free flame retardants and acrylate, prepare preferably engineering plastics of halogen-free flameproof and low-temperature performance.
In the embodiment of the invention:
The molecular weight of polycarbonate is 20000～40000 bisphenol A polycarbonate;
Esters of acrylic acid toughner is the multipolymer of Acrylate-styrene bipolymer-acrylic rubber;
Halogen-free flame retardants is aromatic sulphonate;
Oxidation inhibitor is β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester;
Processing aid is that lubricant pentaerythritol stearate and viscosity are the methyl-silicone oil of 1000CPS.
The low temperature resistant polycarbonate of the halogen-free flameproof of the embodiment of the invention all can adopt same preparation method, may further comprise the steps:
S1. pretreating raw material;
S2. take by weighing each component according to following weight percent:
Polycarbonate 88～95%;
Esters of acrylic acid toughner 4～8%;
Halogen-free flame retardants 0.07～0.1%;
Oxidation inhibitor 0.3～1%;
Processing aid 0.6～0.9%.
All raw materials that S3. will take by weighing mix;
S4. mixing raw material is added parallel double-screw extruder, through melt extruding granulation.
Wherein, the processing condition of parallel double-screw extruder melt stage are in the embodiment of the invention: the screw diameter of parallel double-screw extruder is 35～75 millimeters; In dual-screw-stem machine temperature control section, district's temperature is 220 ℃, and two district's temperature are 240 ℃, and three district's temperature are 255 ℃, four district's temperature are 270 ℃, and five district's temperature are 280 ℃, and six district's temperature are 280 ℃, seven district's temperature are 270 ℃, and eight district's temperature are 270 ℃, and the head temperature of dual-screw-stem machine is 275 ℃; Screw speed is controlled at 250～450r/min; Through the twin screw extruder melt blending extrude, water-cooled, air-dry, pelletizing, last bag becomes the low temperature resistant polycarbonate finished product of halogen-free flameproof.
Embodiment 1:
(1) pretreating raw material: PC and auxiliary agent is dry respectively, and the temperature of PC drying is 100 ℃, 8 hours time; The temperature of all the other auxiliary agent dryings is 65 ℃, 6 hours time.
(2) take by weighing dried PC 95.03kg, esters of acrylic acid toughner 4kg, halogen-free flame retardants 0.07kg, antioxidant 1076 0.1kg, 168 0.2kg, lubricant PETS 0.3kg, silicone oil 0.3KG;
All raw materials that (3) will take by weighing mix 10min in high-speed mixer;
The material that (4) will mix joins in the hopper of twin screw extruder, through the twin screw extruder melt blending extrude, water-cooled, air-dry, pelletizing, last bag becomes finished product.Wherein, screw speed is 250r/min.
Above-mentioned halogen-free flameproof low temperature resistant PC is injection molded into standard test specimen, and test performance is as shown in table 1.
Embodiment 2:
(1) pretreating raw material: PC and auxiliary agent is dry respectively, and the temperature of PC drying is 120 ℃, 4 hours time; The temperature of all the other auxiliary agent dryings is 85 ℃, 3 hours time.
(2) take by weighing dried PC 92.62kg, esters of acrylic acid toughner 6kg, halogen-free flame retardants 0.08kg, antioxidant 1076 0.2kg, 168 0.3kg, lubricant PETS 0.5kg, silicone oil 0.3KG;
All raw materials that (3) will take by weighing mix 20min in high-speed mixer;
The material that (4) will mix joins in the hopper of twin screw extruder, through the twin screw extruder melt blending extrude, water-cooled, air-dry, pelletizing, last bag becomes finished product.Wherein, screw speed is 450r/min.
Above-mentioned halogen-free flameproof low temperature resistant PC is injection molded into standard test specimen, and test performance is as shown in table 1.
Embodiment 3:
(1) pretreating raw material: PC and auxiliary agent is dry respectively, and the temperature of PC drying is 120 ℃, 6 hours time; The temperature of all the other auxiliary agent dryings is 75 ℃, 5 hours time.
(2) take by weighing dried PC 90kg, esters of acrylic acid toughner 8kg, halogen-free flame retardants 0.1kg, antioxidant 1076 0.5kg, 168 0.5kg, lubricant PETS 0.6kg, silicone oil 0.3KG;
All raw materials that (3) will take by weighing mix 15min in high-speed mixer;
The material that (4) will mix joins in the hopper of twin screw extruder, through the twin screw extruder melt blending extrude, water-cooled, air-dry, pelletizing, last bag becomes finished product.Wherein, screw speed is 350r/min.
Above-mentioned halogen-free flameproof low temperature resistant PC is injection molded into standard test specimen, and test performance is as shown in table 1.
Embodiment 4:
(1) pretreating raw material: PC and auxiliary agent is dry respectively, and the temperature of PC drying is 120 ℃, 5 hours time; The temperature of all the other auxiliary agent dryings is 75 ℃, 5 hours time.
(2) take by weighing dried PC 88.8kg, esters of acrylic acid toughner 10kg, halogen-free flame retardants 0.1kg, antioxidant 1076 0.2kg, 168 0.2kg, lubricant PETS 0.4kg, silicone oil 0.3KG;
All raw materials that (3) will take by weighing mix 15min in high-speed mixer;
The material that (4) will mix joins in the hopper of twin screw extruder, through the twin screw extruder melt blending extrude, water-cooled, air-dry, pelletizing, last bag becomes finished product.Wherein, screw speed is 300r/min.
Above-mentioned halogen-free flameproof low temperature resistant PC is injection molded into standard test specimen, and test performance is as shown in table 1.
Embodiment 5:
(1) pretreating raw material: PC and auxiliary agent is dry respectively, and the temperature of PC drying is 120 ℃, 5 hours time; The temperature of all the other auxiliary agent dryings is 75 ℃, 4 hours time.
(2) take by weighing dried PC 95.8kg, esters of acrylic acid toughner 3kg, halogen-free flame retardants 0.1kg, antioxidant 1076 0.2kg, 168 0.2kg, lubricant PETS 0.4kg, silicone oil 0.3KG;
All raw materials that (3) will take by weighing mix 15min in high-speed mixer;
The material that (4) will mix joins in the hopper of twin screw extruder, through the twin screw extruder melt blending extrude, water-cooled, air-dry, pelletizing, last bag becomes finished product.Wherein, screw speed is 300r/min.
Above-mentioned halogen-free flameproof low temperature resistant PC is injection molded into standard test specimen, and test performance is as shown in table 1.
Comparative Examples:
(1) pretreating raw material: PC and auxiliary agent is dry respectively, and the temperature of PC drying is 120 ℃, 4 hours time; The temperature of all the other auxiliary agent dryings is 65 ℃, 6 hours time.
(2) take by weighing dried PC 99kg, antioxidant 1076 0.1kg, 168 0.2kg, lubricant PETS 0.4kg, silicone oil 0.3KG;
All raw materials that (3) will take by weighing mix 10min in high-speed mixer;
The material that (4) will mix joins in the hopper of twin screw extruder, through the twin screw extruder melt blending extrude, water-cooled, air-dry, pelletizing, last bag becomes finished product.Wherein, screw speed is 300r/min.
Above-mentioned PC is injection molded into standard test specimen, and test performance is as shown in table 1.
Table 1 halogen-free flameproof low temperature resistant PC performance table
By the contrast of table 1, the present invention all is better than pure PC on flame retardant resistance (V0 level) and low temperature impact properties, and the shock strength under the pure PC room temperature is higher, but the impact-40 ℃ the time only has 12kj.m
-2, this moment material more crisp, do not have practical value, and improved PC at low temperatures shock strength all greater than 50kj.m
-2, and flame-retardant V 0-stage, can adapt to the high environment of severe cold and electric property.The contriver finds through repetition test, toughner addition 10% and when above, and the mechanical properties decrease of material is obvious, and fire-retardant also influential; When addition was lower than 4%, low-temperature flexibility was improved limited, so 4 ~ 8% addition is proper.
Claims (9)
1. the low temperature resistant polycarbonate of halogen-free flameproof is characterized in that, is made by following material by weight percentage:
Polycarbonate 88～95%;
Esters of acrylic acid toughner 4～8%;
Halogen-free flame retardants 0.07～0.1%;
Oxidation inhibitor 0.3～1%;
Processing aid 0.6～0.9%.
2. the low temperature resistant polycarbonate of a kind of halogen-free flameproof according to claim 1, it is characterized in that: the molecular weight of described polycarbonate is 20000～40000 bisphenol A polycarbonate.
3. the low temperature resistant polycarbonate of a kind of halogen-free flameproof according to claim 1, it is characterized in that: described esters of acrylic acid toughner is the multipolymer of Acrylate-styrene bipolymer-acrylic rubber.
4. the low temperature resistant polycarbonate of a kind of halogen-free flameproof according to claim 1, it is characterized in that: described halogen-free flame retardants is aromatic sulphonate.
5. the low temperature resistant polycarbonate of a kind of halogen-free flameproof according to claim 1, it is characterized in that: described oxidation inhibitor is β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester and tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester.
6. the low temperature resistant polycarbonate of a kind of halogen-free flameproof according to claim 1, it is characterized in that: described processing aid is the PETS(pentaerythritol stearate) and viscosity be the methyl-silicone oil of 1000CPS.
7. the preparation method of the low temperature resistant polycarbonate of halogen-free flameproof is characterized in that, may further comprise the steps:
S1. drying treatment polycarbonate, halogen-free flame retardants, toughner, oxidation inhibitor, processing aid, wherein,
The temperature of dry polycarbonate is 100 ~ 120 ℃, and be 4 ~ 8 hours time of drying;
Dry halogen-free flame retardants, toughner, oxidation inhibitor, processing aid temperature are 65 ~ 85 ℃, and be 3 ~ 6 hours time of drying;
S2. take by weighing each component according to following weight percent:
Polycarbonate 88～95%;
Esters of acrylic acid toughner 4～8%;
Halogen-free flame retardants 0.07～0.1%;
Oxidation inhibitor 0.3～1%;
Processing aid 0.6～0.9%;
All raw materials that S3. will take by weighing mix;
S4. mixing raw material is added parallel double-screw extruder, through melt extruding granulation.
8. the preparation method of the low temperature resistant polycarbonate of halogen-free flameproof according to claim 7 is characterized in that, described step S3 specifically: all raw material stirring that will take by weighing at normal temperatures 10～20 minutes mix.
9. the preparation method of the low temperature resistant polycarbonate of a kind of halogen-free flameproof according to claim 7 is characterized in that the processing condition of melt stage are among the described step S4:
The screw diameter of described parallel double-screw extruder is 35～75 millimeters, and screw slenderness ratio is 36:1;
In dual-screw-stem machine temperature control section, district's temperature is 220 ℃, and two district's temperature are 240 ℃, and three district's temperature are 255 ℃, four district's temperature are 270 ℃, and five district's temperature are 280 ℃, and six district's temperature are 280 ℃, seven district's temperature are 270 ℃, and eight district's temperature are 270 ℃, and the head temperature of dual-screw-stem machine is 275 ℃;
Screw speed is 250～450r/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106398163A (en) * | 2016-09-30 | 2017-02-15 | 福建华塑新材料有限公司 | Low temperature resistant and high impact resistant polycarbonate and preparation method thereof |
| CN109610754A (en) * | 2018-12-06 | 2019-04-12 | 嘉兴领科材料技术有限公司 | A kind of aviation interior trim flame-retarding high performance wallpaper and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417704A (en) * | 2011-10-10 | 2012-04-18 | 福建奥峰科技有限公司 | Weather-resistant flame-retardant polycarbonate (PC) composition, and preparation method and application thereof |
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- 2012-12-20 CN CN2012105598968A patent/CN103044885A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102417704A (en) * | 2011-10-10 | 2012-04-18 | 福建奥峰科技有限公司 | Weather-resistant flame-retardant polycarbonate (PC) composition, and preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106398163A (en) * | 2016-09-30 | 2017-02-15 | 福建华塑新材料有限公司 | Low temperature resistant and high impact resistant polycarbonate and preparation method thereof |
| CN109610754A (en) * | 2018-12-06 | 2019-04-12 | 嘉兴领科材料技术有限公司 | A kind of aviation interior trim flame-retarding high performance wallpaper and preparation method thereof |
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Application publication date: 20130417 |