CN107641308A - A kind of Halogen-free intumescent flame retardant polycarbonate composition and preparation method thereof - Google Patents
A kind of Halogen-free intumescent flame retardant polycarbonate composition and preparation method thereof Download PDFInfo
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- CN107641308A CN107641308A CN201710931319.XA CN201710931319A CN107641308A CN 107641308 A CN107641308 A CN 107641308A CN 201710931319 A CN201710931319 A CN 201710931319A CN 107641308 A CN107641308 A CN 107641308A
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Abstract
The invention discloses a kind of Halogen-free intumescent flame retardant polycarbonate composition and preparation method thereof, belongs to macromolecule modified technical field.With the following raw material formula：100 parts of polycarbonate resin, 0.01 30 parts of halogen-free expansion fire retardant, 0.1 1 parts of anti-dripping agent, antioxidant：0.2 2 parts, 0.01~10 part of other auxiliary agents.Instant invention overcomes harm of the halogen flame to environment and human body is added in makrolon, phosphorus nitrogen silicon cooperative flame retardant effect improves the fire resistance of makrolon in phosphonitrile analog derivative, VL 94V 0 can be reached, and only need to add phosphazene derivative fire retardant on a small quantity, good flame retardant effect can be reached, substantially reduce production cost.
Description
Technical field
The invention belongs to macromolecule modified technical field, more specifically to a kind of halogen-free expansion type flame-proof makrolon
Composition and preparation method thereof.
Background technology
Makrolon (PC) has excellent translucency, higher impact strength and glass transition temperature, preferably electricity
Insulating properties, weatherability etc., it is widely used in building, electronic electric equipment, traffic, optics etc..Because makrolon is easy
Combustion, limits its application field, therefore, it is necessary to be carried out to it flame-retardant modified significantly.
Once the halogenated flame retardant of extensive utilization was although cheap, but can generate toxic gas, carcinogenic in combustion
Material etc., cause secondary pollution, and endanger human body health, therefore, halogenated flame retardant is worldwide by progressively quiet
Only use.Therefore, the research and development of novel halogen-free flame-retardant agent enjoy favor.
It is inorganic respectively to have advantage and disadvantage with organic fire-retardant.Inorganic combustion inhibitor is cheap, environmental protection, but with the compatibility of organic polymer
Poor, the shortcomings of interface binding power is small, bad dispersibility, so as to influence its flame retardant effect.And organic fire-retardant exist poor heat resistance,
Burning has the shortcomings that drippage.Therefore both are combined, the advantage and disadvantage of the BACN of gained mutually make up, and are reached so as to be made
To the more preferable BACN of flame retardant effect.
Ring phosphazene derivative fire retardant is a kind of typical organic --- inorganic hybridization fire retardant, the advantages of there are both,
Its fire resistance is also inestimable, therefore the research for the phosphazene derivative fire retardant of ring three is necessary.China is
The patent for much studying this based flame retardant is disclosed, such as enters the preparation of the hexaphenoxycyclotriphosphazene of business neighborhood.Phosphonitrile spreads out
Biology is added to research in epoxy resin it has been reported that still as fire retardant main body as flame retardant synergistic composition
The research that composition is applied in makrolon is still rare.
The content of the invention
A kind of Halogen-free intumescent flame retardant polycarbonate composition, is counted in parts by weight, has the following raw material formula：
Polycarbonate resin：100 parts；
Halogen-free expansion fire retardant：0.01-10 parts；
Anti-dripping agent：0.1-1 parts；
Antioxidant：0.2-2 parts；
Other auxiliary agents：0.01~10 part.
The makrolon is aromatic copolycarbonate (makrolon of the main chain containing only aryl, such as bisphenol-a polycarbonate)
Or aromatic copolycarbonate gathers with fatty poly-ester carbonate (main chain comprises only the makrolon of fat-based), aromatic-aliphatic
Carbonic ester (the not only makrolon containing aryl but also containing fat-based in main chain), branching polycarbonate (contain different chains in main chain
The makrolon of long side chain) at least one of mixture.
The halogen-free expansion fire retardant is the phosphorus-nitrogen containing silicon fire retardant with following structural formula：
Wherein x=1-5, y=1-5, x+y=6, n=3~11.
The anti-dripping agent is polytetrafluoroethylene (PTFE).
The antioxidant is three [2,4- di-tert-butyl-phenyls] phosphite esters, β-(3,5- di-tert-butyl-hydroxy phenyls)
The positive octadecanol ester of propionic acid, four [(2,4- di-tert-butylphenols) -4,4 ' xenyls] diphosphites or four [β-(bis- tertiary fourths of 3,5-
Base -4- hydroxy phenyls) propionic acid] one or more in pentaerythritol ester.
Other auxiliary agents are heat stabilizer (such as barium zinc compound), light stabilizer (such as carbon black), plasticizer (such as adjacent benzene two
Formic acid two (2- ethyl hexyls) ester), colouring agent (such as titanium dioxide), at least one of filler (such as talcum powder).
A kind of preparation method of above-mentioned Halogen-free intumescent flame retardant polycarbonate composition, is followed the steps below：
After makrolon, fire retardant, anti-dripping agent, antioxidant and other auxiliary agents are sufficiently mixed in high-speed mixer,
Halogen-free intumescent flame retardant polycarbonate composition is obtained after double screw extruder extruding pelletization.
The beneficial effects of the invention are as follows：The phosphazene derivative of Nitrogen-and Phosphorus-containing silicon ring three combines the advantages of inorganic, organic fire-retardant,
Harm of the halogen flame to environment and human body is added in makrolon in use, overcoming as fire retardant, and in condensed phase
It is middle to form fine and close foamed char, effective starvation and calorie spread, so as to improve the anti-flammability of polymeric material.In addition,
Phosphorus-nitrogen-silicon cooperative flame retardant effect improves the fire resistance of makrolon in Nitrogen-and Phosphorus-containing silicon phosphazene derivative, and adds on a small quantity certainly
The fire retardant of system can be to reach UL-94V-0, so as to substantially reduce production cost.
Embodiment
With reference to embodiments, the present invention will be described in further detail, and specific embodiment described herein is only
To explain the present invention, it is not intended to limit the present invention.
The invention discloses a kind of halogen-free flame-retardant polycarbonate composition and preparation method thereof, through the application preparation method system
The polycarbonate compositions obtained have the characteristics that excellent heat resistance, flame retardant rating；It realizes that reason is, the present invention is poly- to this
The composition of raw materials of carbonate composition optimizes combination, and is equipped with and innovation is optimized to its preparation method, illustrate as
Under：
(1) preparation of polycarbonate compositions master batch
Embodiment 1~6 is prepared all in accordance with weight percentage shared by the raw material described in table 1, and according to following steps
Polycarbonate compositions master batch：Makrolon, halogen-free expansion fire retardant, anti-dripping agent and the antioxidant of formula ratio are weighed, is thrown
Enter after being sufficiently mixed into high-speed mixer, through double screw extruder extruding pelletization, obtain polycarbonate compositions master batch.
In addition, in the present invention, the makrolon is aromatic copolycarbonate or aromatic copolycarbonate and aliphatic
The mixture of at least one of makrolon, aromatic-aliphatic makrolon, branching polycarbonate.
The halogen-free expansion fire retardant is the phosphorous nitrogen combustion inhibitor with following structural formula：
Wherein x=1-5, y=1-5, x+y=6, n=3~11.
The anti-dripping agent is polytetrafluoroethylene (PTFE).
The antioxidant is three [2,4- di-tert-butyl-phenyls] phosphite esters, β-(3,5- di-tert-butyl-hydroxy phenyls)
The positive octadecanol ester of propionic acid, four [(2,4- di-tert-butylphenols) -4,4 ' xenyls] diphosphites or four [β-(bis- tertiary fourths of 3,5-
Base -4- hydroxy phenyls) propionic acid] one or more in pentaerythritol ester.
Other auxiliary agents are at least one of heat stabilizer, light stabilizer, plasticizer, filler, colouring agent.
Table 1：Unit：Mass fraction
(2) test of product fire resistance
According to professional standard, it is fire-retardant that UL-94 is carried out to the polycarbonate compositions obtained by above-described embodiment 1~6 respectively
Property test.Wherein, the standard of UL-94 anti-flammabilitys test is：
According to " the flammable of plastic material is tested, and UL-94 " code carries out flammable test.Based on burn rate, put out
Go out the time, resistance drippage ability and drippage whether just burning, to draw flame retardant rating.Sample for test：Size is
125mm length × 13mm width × be not more than 13mm thickness rod, the present invention when being tested the thickness of rod elect 1.5mm as.
According to the UL-94 codes, and based on the test result obtained for five samples, material flame retardant rating can be categorized as：V-
0、V-1、V-2、5VA、5VB；But in the present invention, only the flame retardant rating of material is categorized as：V-0, V-1, V-2, and it is each fire-retardant
The criteria for classification of grade is：
V-0:In placing and causing sample that its major axis relative to flame is 180 degree, after flame is lighted in removing, burning or
The time is smouldered no more than 10 seconds, and the sample being disposed vertically is without the drippage for the burning particles for producing the absorbent cotton that ignites.First
Flame out time (the t lighted1) and the second flame out time (t lighted2) summation (be maximum flame out time (t1+t2)) be less than
Or equal to 50 seconds.
V-1:In placing and causing sample that its major axis relative to flame is 180 degree, after flame is lighted in removing, burning or
The time is smouldered no more than 30 seconds, and the sample being disposed vertically is without the drippage for the burning particles for producing the absorbent cotton that ignites.First
Flame out time (the t lighted1) and the second flame out time (t lighted2) summation (be maximum flame out time (t1+t2)) be less than
Or equal to 250 seconds.
V-2:In placing and causing sample that its major axis relative to flame is 180 degree, after flame is lighted in removing, burning or
The time is smouldered no more than 30 seconds, and the sample being disposed vertically produces the drippage of the burning particles for the absorbent cotton that ignites.First lights
Flame out time (t1) and the second flame out time (t lighted2) summation (be maximum flame out time (t1+t2)) be less than or wait
In 250 seconds.
Table 2：The test result of the anti-flammability of polycarbonate compositions obtained by the embodiment of the present invention 1~6
Claims (7)
1. a kind of Halogen-free intumescent flame retardant polycarbonate composition, it is characterised in that count, match somebody with somebody with the following raw material in parts by weight
Side：
Polycarbonate resin：100 parts；
Halogen-free expansion fire retardant：0.01-10 parts；
Anti-dripping agent：0.1-1 parts；
Antioxidant：0.2-2 parts；
Other auxiliary agents：0.01~10 part.
A kind of 2. Halogen-free intumescent flame retardant polycarbonate composition according to claim 1, it is characterised in that the poly- carbon
Acid esters is aromatic copolycarbonate or aromatic copolycarbonate and fatty poly-ester carbonate, aromatic-aliphatic makrolon, branch
Change the mixture of at least one of makrolon.
A kind of 3. Halogen-free intumescent flame retardant polycarbonate composition according to claim 1, it is characterised in that the Halogen
Expansion type flame retardant is the phosphorous nitrogen combustion inhibitor with following structural formula：
Wherein x=1-5, y=1-5, x+y=6, n=3~11.
A kind of 4. Halogen-free intumescent flame retardant polycarbonate composition according to claim 1, it is characterised in that the anti-drop
It is polytetrafluoroethylene (PTFE) to fall agent.
A kind of 5. Halogen-free intumescent flame retardant polycarbonate composition according to claim 1, it is characterised in that the antioxygen
Agent be three [2,4- di-tert-butyl-phenyls] phosphite esters, the β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid,
Four [(2,4- di-tert-butylphenols) -4,4 ' xenyls] diphosphites or four [β-(3,5- di-tert-butyl-hydroxy phenyls) third
Acid] one or more in pentaerythritol ester.
6. a kind of Halogen-free intumescent flame retardant polycarbonate composition according to claim 1, it is characterised in that described other
Auxiliary agent is at least one of heat stabilizer, light stabilizer, plasticizer, filler, colouring agent.
7. a kind of preparation method of Halogen-free intumescent flame retardant polycarbonate composition according to claim 1, its feature exist
In comprising the following steps：By makrolon, fire retardant, anti-dripping agent, antioxidant and other auxiliary agents in high-speed mixer fully
After mixing, Halogen-free intumescent flame retardant polycarbonate composition is obtained after double screw extruder extruding pelletization.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558187A (en) * | 2022-11-09 | 2023-01-03 | 唐山工业职业技术学院 | Novel expansion flame-retardant wood-plastic composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
| CN105481899A (en) * | 2015-11-27 | 2016-04-13 | 长沙欧赛新材料有限公司 | Novel halogen-free cyclotriphosphazene compound and its preparation method and use |
-
2017
- 2017-10-09 CN CN201710931319.XA patent/CN107641308A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250147A (en) * | 2011-05-17 | 2011-11-23 | 北京理工大学 | Preparation method and application of cyclotriphosphazene containing silicon functional groups |
| CN105481899A (en) * | 2015-11-27 | 2016-04-13 | 长沙欧赛新材料有限公司 | Novel halogen-free cyclotriphosphazene compound and its preparation method and use |
Non-Patent Citations (1)
| Title |
|---|
| 贺攀: "含硅磷腈阻燃剂的合成及其阻燃性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115558187A (en) * | 2022-11-09 | 2023-01-03 | 唐山工业职业技术学院 | Novel expansion flame-retardant wood-plastic composite material and preparation method thereof |
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Application publication date: 20180130 |