CN109535683A - Fire retardant polycarbonate compositions and preparation method thereof - Google Patents
Fire retardant polycarbonate compositions and preparation method thereof Download PDFInfo
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- CN109535683A CN109535683A CN201811446382.5A CN201811446382A CN109535683A CN 109535683 A CN109535683 A CN 109535683A CN 201811446382 A CN201811446382 A CN 201811446382A CN 109535683 A CN109535683 A CN 109535683A
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The present invention provides a kind of fire retardant polycarbonate compositions and preparation method thereof, wherein, fire retardant polycarbonate compositions, each component including following parts by weight: 96.0-99.8 parts of polycarbonate resin, 0.1-3.0 parts of toughener, 0.01-6.0 parts of fire retardant, 0.1-5.0 parts of anti-hydrolysis agent, 0.01-2.0 parts of antioxidant, 0.01-1.2 parts of other auxiliary agents；Wherein, anti-hydrolysis agent is one of carbodiimides, isocyanates, oxazoline, epoxide.Fire retardant polycarbonate compositions of the present invention have preferable flame retardant property, toughness and hydrolytic Resistance, and heat resisting temperature is higher than 120 DEG C, and relatively high occasion is required especially suitable for use environment.
Description
Technical field
The invention belongs to engineering plastics technical fields, more particularly, to a kind of fire retardant polycarbonate compositions and its preparation
Method.
Background technique
Polycarbonate resin is a kind of general engineering plastic, has the transparency, impact resistance, heat resistance, dimensional stability
Etc. various aspects the advantages of, and due to its above-mentioned excellent characteristic, be industrially widely used as the office such as automotive field, printer
Apparatus field, mobile phone etc. be electrical, electronic field material.The common polycarbonate of existing market is using interface polycondensation
Preparation, wherein containing a large amount of ester group.Higher or when relative humidity is larger in temperature, water holds with the help of heat and oxygen
It easily reacts and degrades with polycarbonate, the hydroperoxyl radical for generation of degrading further is catalyzed the fracture of polycarbonate strand.
Resin mechanical performance decline after hydrolysis, seriously affects it in the use of some specific areas.
In addition needing fire-retardant application field, PC often have many advantages, such as with phosphate flame retardant it is environmentally friendly, fire-retardant efficient, but
Be it addition usually to PC generate plasticization, influence the toughness and heat resistance of PC resin.In addition in the ring of high temperature and humidity
It under border, is easier to cause the degradation of PC using phosphate flame retardant, therefore, aromatic phosphate acid ester flame retardant is under hot and humid environment
Using being restricted.
Summary of the invention
In view of this, the present invention is directed to propose a kind of fire retardant polycarbonate compositions, to overcome the deficiencies of existing technologies,
With preferable flame retardant property, toughness and hydrolytic Resistance, and heat resisting temperature is higher than 120 DEG C, wants especially suitable for use environment
Seek relatively high occasion.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
Fire retardant polycarbonate compositions, each component including following parts by weight:
96.0-99.8 parts of polycarbonate resin, 0.1-3.0 parts of toughener, 0.01-6.0 parts of fire retardant, anti-hydrolysis agent 0.1-
5.0 parts, 0.01-2.0 parts of antioxidant, 0.01-1.2 parts of other auxiliary agents；Wherein, anti-hydrolysis agent be carbodiimides, isocyanates,
One of oxazoline, epoxide.
Preferably, the fire retardant polycarbonate compositions, each component including following parts by weight: polycarbonate resin
96.0-99.8 parts, 0.1-3.0 parts of toughener, 0.01-5.0 parts of fire retardant, 0.1-2.0 parts of anti-hydrolysis agent, antioxidant 0.01-2.0
Part, 0.01-1.2 parts of other auxiliary agents；Wherein, anti-hydrolysis agent is carbodiimides, in isocyanates, oxazoline, epoxide
One kind.
Preferably, anti-hydrolysis agent is carbodiimides, and the main component of carbodiimides is the oligomer of carbodiimides,
Since easily with the active hydrogen reaction that generates in PC degradation process, the degradation of PC can be prevented in time, while can also effectively improve
The thermal stability of PC.
Preferably, other described auxiliary agents, which can according to need, is properly added, such as may include lubricant, anti-dripping agent,
Wherein lubricant and anti-dripping agent can be added individually or be added jointly.Lubricant is tristerin, and anti-dripping agent is selected
The PTFE of AS cladding lid.Preferably, antioxidant is the primary antioxidant and auxiliary anti-oxidant group of 1.0:(0.5-1.0) by quality proportioning
At；Primary antioxidant and auxiliary anti-oxidant are acrylic ester kind antioxidant, can include but is not limited to octadecyl -3- (3,5- bis--uncles
Butyl -4- hydroxy phenyl) propionic ester；Phosphite ester antioxidant, can include but is not limited to three (nonyl phenyl) phosphite esters,
Bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, distearyl pentaerythrityl diphosphite；Alkylated list
The alkylated reaction product of phenol or polyphenol, polyphenol and diene, such as four [methylene (3,5- di-t-butyl -4- hydroxy group cortex cinnamomis
Acid esters)] methane, paracresol or bicyclopentadiene butylated reaction product；Alkylated hydroquinone；It is hydroxylated thio
Diphenyl ether；Alkylidenebisphenols；Benzyl compounds；β-(3,5- di-t-butyl -4- hydroxy phenyl)-propionic acid and unitary or polyalcohol
Ester；The ester of β-(5- tertiary butyl-4-hydroxy -3- aminomethyl phenyl)-propionic acid and unitary or polyalcohol；Alkylthio or thioaryl
The ester of compound, such as distearyl thiopropionate, dilauryl thiopropionate, tricosyl thiodipropionate, season
- four [3- (3,5- di-t-butyl 4- hydroxy phenyl) propionic ester of penta 4 alcohol radicals；β-(3,5- di-t-butyl -4- hydroxy phenyl)-the third
The amide of acid, or the combination including at least one of above-mentioned antioxidant.
Preferably, the polycarbonate resin refer to aromatic hydroxy compound reacted with phosgene or carbonic diester or virtue
The thermoplasticity with branch that fragrant race's hydroxy compounds and a small amount of polyol are reacted with phosgene or carbonic diester
Aromatic polycarbonate polymers or copolymer.The manufacturing method of above-mentioned aromatic polycarbonate resin is not particularly limited, can
Using currently known technical method, such as phosgenation (interfacial polymerization), fusion method (ester-interchange method).Outside to formed body
It sees and mobility improves, the molecular weight of heretofore described polycarbonate resin suitably selects, and is viscosity average molecular weigh
At least one of aromatic copolycarbonate of 10000-40000.The above-mentioned viscosity average molecular weigh to be converted by solution viscosity
[Mv] is usually 10000 or more, preferably 12000 or more, and usually 40000 hereinafter, preferably 30000 hereinafter, more preferably
It is 25000 or less.By the way that viscosity average molecular weigh is set as in aforementioned range, it is ensured that polycarbonate resin composition of the invention
The mechanical strength of object is the height it is furthermore preferred that when in addition can guarantee shaping thin wall in the purposes high for requirement of mechanical strength
Mobility.That is, polycarbonate resin is at least one of the aromatic copolycarbonate of viscosity average molecular weigh 10000-40000；
Preferably, polycarbonate resin is at least one of the aromatic copolycarbonate of viscosity average molecular weigh 12000-30000；More preferably
, the polycarbonate resin is at least one of the aromatic copolycarbonate of viscosity average molecular weigh 12000-25000.
Preferably, toughener is Methyl Methacrylate-Butadiene-Styrene Copolymer, methyl methacrylate-propylene
Acid copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylate-methacrylic acid
Ethylene oxidic ester terpolymer, the ethylene-vinyl acetate copolymer of maleic anhydride functional, acrylic compounds toughener and organic
At least one of silicon rubber graft toughener；Preferably, toughener is organic silicon rubber graft toughener, and the toughening
In agent the volume average particle size of rubber constituent be 200-2000nm, preferably 220-1500nm, more preferably 280-1000nm, into
One step is preferably 350-800nm.By making the volume average particle size of rubber constituent within the scope of 350-800nm, can be obtained preferably
Impact resistance and influence small resin combination to fire-retardant.If the volume average particle size of rubber constituent is in 350nm or more, resin
The impact resistance of composition becomes well, is preferred；And if the volume average particle size of rubber constituent in 600nm hereinafter, right
The influence of resin combination flame retardant property is smaller.
Preferably, fire retardant be halogen based flame retardant, phosphorus flame retardant, type siloxane fire retardant, metallic salt fire retardant,
One of boryl fire retardant.
Preferably, fire retardant is metallic salt fire retardant, and metal organic sulfonate fire retardant in metallic salt fire retardant
It is preferred.Metal in metal organic sulfonate is alkali or alkaline earth metal；Preferably, alkali metal is lithium (Li), sodium
(Na), one of potassium (K), rubidium (Rb), caesium (Cs)；It is furthermore preferred that alkali metal is sodium (Na), potassium (K) or caesium (Cs), most preferably
Alkali metal be potassium (K)；Preferably, alkaline-earth metal is beryllium, magnesium (Mg), calcium (Ca), strontium or barium.
The fire retardant can preferably be promoted with the introducing for metal organic sulfonate fire retardant, metal organic sulfonate fire retardant
Into the formation of polycarbonate resin carburization zone during burning, thus the anti-flammability of polycarbonate can be improved well, it can be with
The excellent horizontal property for maintaining polycarbonate to possess, such as electrical properties, heat resistance, impact resistance.To metal organic sulfonate
In metal be not particularly limited, but preferably metal such as sodium, lithium, potassium or caesium or alkaline-earth metal such as beryllium, magnesium, calcium, strontium or barium.But
From the aspect of anti-flammability and hydrolytic resistance, preferred potassium.
Preferably, fire retardant is metal organic sulfonate fire retardant, and wherein metal organic sulfonate is fluorine-containing aliphatic sulphur
The metal salt of acid, the metal salt of fluorine-containing aromatic sulphonimides, the metal salt of aromatic sulfonic acid or aromatic sulfonamides metal salt；It is preferred that
, metal organic sulfonate is the metal salt of fluorine-containing aliphatic sulfonic and metal salt (the organic sulphur of such as diphenyl sulfone of aromatic sulfonic acid
Acid metal salt, full phenyl butane potassium sulfonate)；More there is choosing, metal organic sulfonate is the metal salt of fluorine-containing aliphatic sulfonic, and
The metal salt of fluorine-containing aliphatic sulfonic is the alkali metal salt of the fluorine-containing aliphatic sulfonic in molecule comprising at least one C-F key, than
As potassium perfluorobutane sulfonate, lithium perfluorobutane, perfluorinated butane conversion caesium, trifluoromethayl sulfonic acid lithium, trifluoromethayl sulfonic acid sodium,
Trifluoromethayl sulfonic acid potassium, pentafluoroethane potassium sulfonate, heptafluoro-propane potassium sulfonate and ten fluoro- 4- (pentafluoroethyl group) cyclohexanesulfonics
Potassium etc., particularly preferably potassium perfluorobutane sulfonate.
Preferably, the fire retardant polycarbonate compositions, each component including following parts by weight: polycarbonate resin
96.0-99.8 parts, 0.1-3.0 parts of toughener, 0.01-2.0 parts of fire retardant, 0.01-2.0 parts of antioxidant；Lubricant 0.05-0.3
Part；0.1-0.6 parts of anti-dripping agent；
Wherein, polycarbonate resin is Mitsubishi S-3000F polycarbonate resin, and toughener is the beautiful sun of Mitsubishi
SX-005 toughener, fire retardant are Mitsubishi EF-42 fire retardant, and anti-hydrolysis agent is German Rhine chemistry Stabaxol P water resistant
Agent is solved, antioxidant is by primary antioxidant Chinox 1076 and the 1.0:(0.5-1.0 in mass ratio of auxiliary anti-oxidant THANOX 168) mixing
It forms, lubricant UNISTER-M9676, anti-dripping agent A3800.
Another object of the present invention is to propose a kind of method for preparing fire retardant polycarbonate compositions as described above,
To prepare above-mentioned fire retardant polycarbonate compositions.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of preparation method of fire retardant polycarbonate compositions, comprising the following steps:
(1) weighed respectively by formulation dosage polycarbonate resin, toughener, fire retardant, anti-hydrolysis agent, antioxidant and other
After auxiliary agent, above-mentioned raw materials are successively put into mixing machine and are blended into uniformly, pre-composition is obtained；
(2) it will be prepared in step (1) in resulting pre-composition investment double screw extruder, the spiral shell of the double screw extruder
Bar draw ratio is 40-45:1, and barrel temperature is 250-280 DEG C, screw speed 400-500rpm；The pre-composition is in double spiral shells
Melting mixing and extruding pelletization, are made the fire retardant polycarbonate compositions in bar extruder.
Compared with the existing technology, fire retardant polycarbonate compositions of the present invention have the advantage that
Fire retardant polycarbonate compositions of the present invention select the fire retardant for not influencing polycarbonate heat resisting temperature,
Promote flame retardant property greatly, add preferred toughener can not only supplement composition toughness and reduce to the greatest extent
Influence to flame retardant property, in combination with the use of anti-hydrolysis agent, coordination plasticizing agent greatly improve polycarbonate it is damp and hot after
Toughness retains.Resulting composition is prepared with preferable flame retardant property, toughness and hydrolytic Resistance, and heat resisting temperature is higher than
120 DEG C, relatively high occasion is required especially suitable for use environment.
The preparation method of the fire retardant polycarbonate compositions of described one kind is opposite with above-mentioned fire retardant polycarbonate compositions
The advantage possessed by the prior art is identical, and details are not described herein.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to embodiment, the present invention will be described in detail.
In 1-3 of the embodiment of the present invention and comparative example 1-5: polycarbonate resin (PC resin) selection viscosity average molecular weigh is
22000 PC S-3000F (Mitsubishi)；Toughener selects the SX-005 of the beautiful sun of Mitsubishi, other toughener select Japan
The S-2001 of the beautiful sun of Mitsubishi；Fire retardant selects EF-42 (Mitsubishi), other fire retardants select the (Jiangsu PhireGuard BDP
Ya Ke)；Anti-hydrolysis agent selects Stabaxol P (German Rhine chemistry).Lubricant in other auxiliary agents selects UNISTER-
M9676 (Japanese day oil)；Anti-dripping agent in other auxiliary agents selects A3800 (the beautiful sun of Mitsubishi).Antioxidant is by primary antioxidant and auxiliary
Antioxidant composition, wherein primary antioxidant selects AO1076, the i.e. positive octadecanol of β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid
Ester (CAS NO.: (2082-79-3)), auxiliary anti-oxidant select THANOX 168, and the quality proportioning of primary antioxidant and auxiliary anti-oxidant is
1.0:0.6.
Polycarbonate resin, toughener, fire retardant, resistant to hydrolysis are weighed respectively according to each raw material dosage in formula described in table 1
It successively puts into mixing machine and is blended into uniformly after agent, antioxidant and other auxiliary agents, obtain pre-composition；Then pre-composition is put into double
Melting mixing and extruding pelletization are carried out in screw extruder, and the fire retardant polycarbonate compositions are made.Wherein twin-screw squeezes
The screw slenderness ratio of machine is 40:1 out, and barrel temperature is 260~280 DEG C, and screw speed is 400~500rpm.
The melt of progress high heat and humidity before and after the processing is tested respectively to resulting fire retardant polycarbonate compositions are prepared
The measurement of flow rate, notched Chalpy impact intensity and anti-flammability, wherein high heat and humidity treatment conditions are water and hot common point
Experiment condition is managed, specifically: 300h is handled under 85 DEG C, 85% humidity.Melt flow rate (MFR), notched Chalpy impact intensity and
The test institute's reference standard or method of the measurement of anti-flammability are as described below.
(1) measuring method of melt flow rate (MFR) (MFR).Allow plastic pellet in certain time (10 minutes), certain temperature
And (a variety of materials standard is different) are melted into plastic liquid under pressure, then measurement is flowed out by a diameter by 2.1mm round tube
Grams.The grams value of outflow is bigger, indicates that the processing fluidity of the plastic material is better, on the contrary then poorer；It is adopted in the present invention
It is ISO 1133, unit: g/10min with testing standard.Using test condition are as follows: the melt flow under 300 DEG C, 1.2kg load
Dynamic rate (MFR).
(2) measuring method of cantilever beam impact strength: notch is measured using the molding notched Chalpy impact stick of 4.0mm thickness
Cantilever beam impact strength.Notched Chalpy impact intensity is measured according to ISO 180, with kJ/m2Record is as a result, test in room temperature
It is carried out under (23 DEG C).
(3) measuring method of UL94 anti-flammability:
According to " the flammable test of plastic material, the regulation of UL94 " carry out flammable test.Based on burn rate, extinguish
Time resists the ability dripped and falls whether drop (drip) is just burning, to obtain flame retardant rating.Sample for test: ruler
The very little stick for 125mm length × 13mm width × be not more than 13mm thickness, the thickness of present invention stick when testing are selected as
2.0mm.According to the UL94 regulation, and based on the test result obtained for five samples, material flame retardant rating can be classified
For (UL94-HB): V0, V1, V2,5VA and/or 5VB；But in the present invention, only the flame retardant rating of material is classified are as follows: V0, V1
And V2, and the classification standard of each flame retardant rating are as follows:
V0: placing so that in the sample that its long axis is 180 degree relative to flame, after flame is lighted in removing, burning and/
Or the period smouldered is no more than 10 seconds, and the sample being disposed vertically does not generate the drippage of the burning particles for the absorbent cotton that ignites.
The flame out time of 5th stick is the flame out time of five sticks, is each lighted twice, wherein the first flame out time (t1) lighted
The summation (as maximum flame out time (t1+t2)) for the flame out time (t2) lighted with second is less than or equal to 50 seconds.
V1: placing so that in the sample that its long axis is 180 degree relative to flame, after flame is lighted in removing, burning and/
Or the period smouldered is no more than 30 seconds, and the sample being disposed vertically does not generate the drippage of the burning particles for the absorbent cotton that ignites.
The flame out time of 5th stick is the flame out time of five sticks, is each lighted twice, wherein the first flame out time (t1) lighted
The summation (as maximum flame out time (t1+t2)) for the flame out time (t2) lighted with second is less than or equal to 250 seconds.
V2: placing so that in the sample that its long axis is 180 degree relative to flame, after flame is lighted in removing, burning and/
Or the Average Life smouldered is no more than 30 seconds, but the sample being disposed vertically generates the drippage of the burning particles for cotton of igniting.5th
The flame out time of a stick is the flame out time of five sticks, is each lighted twice, wherein the first flame out time (t1) lighted and
The summation (as maximum flame out time (t1+t2)) of two flame out times (t2) lighted is less than or equal to 250 seconds.
Above-mentioned test result is referring to table 2.
1~5 dosage of 1 Examples 1 to 3 of table and comparative example (unit: parts by weight)
1~5 the performance test results of 2 Examples 1 to 3 of table and comparative example
As can be seen from Table 2, compared with the composite material obtained by the comparative example 1~5 of specific embodiment 1~3, comparative example 1
The high heat and humidity of polycarbonate compositions obtained by~5 ISO notch impact strength before and after the processing and flame retardant property are or high
Or low variation, high tenacity and fire-retardant requirement under Special use environment cannot be met simultaneously.Different from comparative example 1~5, originally
The fire retardant that fire retardant polycarbonate compositions use obtained by inventive embodiments is organic metal sulfonate salt flame, in spy
With the help of different toughener and anti-hydrolysis agent, high heat and humidity treated toughness and flame retardant property are maximally maintained.
Fire retardant polycarbonate compositions product obtained by the present invention can be widely applied to such as household electrical appliance, wall and open
Pass, kitchen appliance, house material, automotive material and component manufacture material of other industrial circles etc., especially suitable for family
Outside, the harsh application field such as ship.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. fire retardant polycarbonate compositions, it is characterised in that: each component including following parts by weight:
96.0-99.8 parts of polycarbonate resin, 0.1-3.0 parts of toughener, 0.01-6.0 parts of fire retardant, anti-hydrolysis agent 0.1-5.0
Part, 0.01-2.0 parts of antioxidant, 0.01-1.2 parts of other auxiliary agents；Wherein, anti-hydrolysis agent is carbodiimides, isocyanates, evil
One of oxazoline, epoxide.
2. fire retardant polycarbonate compositions according to claim 1, it is characterised in that: each group including following parts by weight
Point: 96.0-99.8 parts of polycarbonate resin, 0.1-3.0 parts of toughener, 0.01-5.0 parts of fire retardant, anti-hydrolysis agent 0.1-2.0
Part, 0.01-2.0 parts of antioxidant, 0.01-1.2 parts of other auxiliary agents；Wherein, anti-hydrolysis agent is carbodiimides, isocyanates, evil
One of oxazoline, epoxide.
3. fire retardant polycarbonate compositions according to claim 1 or 2, it is characterised in that: anti-hydrolysis agent is carbonization two
Imines；Other auxiliary agents are lubricant and/or anti-dripping agent；Lubricant is tristerin, and anti-dripping agent selects AS cladding lid
PTFE.
4. fire retardant polycarbonate compositions according to claim 3, it is characterised in that: polycarbonate resin is viscous divides equally
At least one of the aromatic copolycarbonate of son amount 10000-40000；Preferably, polycarbonate resin is viscosity average molecular weigh
At least one of aromatic copolycarbonate of 12000-30000；It is furthermore preferred that the polycarbonate resin is viscosity average molecular weigh
At least one of aromatic copolycarbonate of 12000-25000.
5. fire retardant polycarbonate compositions according to claim 3, it is characterised in that: toughener is methyl methacrylate
Ester-butadiene-styrene copolymer, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, second
Alkene-butyl acrylate copolymer, ethylene-acrylate-glycidyl methacrylate terpolymer, maleic anhydride function
At least one of ethylene-vinyl acetate copolymer, acrylic compounds toughener and organic silicon rubber graft toughener of change；It is excellent
Choosing, toughener is organic silicon rubber graft toughener, and the volume average particle size of rubber constituent is 200- in the toughener
2000nm；It is furthermore preferred that toughener is organic silicon rubber graft toughener, the volume of rubber constituent is averaged grain in the toughener
Diameter is 350-800nm.
6. fire retardant polycarbonate compositions according to claim 3, it is characterised in that: fire retardant is that halogen is fire-retardant
One of agent, phosphorus flame retardant, type siloxane fire retardant, metallic salt fire retardant, boryl fire retardant；Preferably, fire retardant
For metallic salt fire retardant；It is furthermore preferred that fire retardant is metal organic sulfonate fire retardant, and the gold in metal organic sulfonate
Belonging to is alkali or alkaline earth metal；Preferably, alkali metal be one of lithium, sodium, potassium, rubidium, caesium, preferred alkali metal be sodium,
Potassium or caesium, most preferred alkali metal are potassium；Preferably, alkaline-earth metal is beryllium, magnesium, calcium, strontium or barium.
7. fire retardant polycarbonate compositions according to claim 3, it is characterised in that: fire retardant is organic sulfonic acid metal
Salt fire retardant, wherein metal organic sulfonate be the metal salt of fluorine-containing aliphatic sulfonic, fluorine-containing aromatic sulphonimides metal salt,
The metal salt of aromatic sulfonic acid or the metal salt of aromatic sulfonamides；Preferably, metal organic sulfonate is fluorine-containing aliphatic sulfonic
The metal salt of metal salt and aromatic sulfonic acid；More there is choosing, metal organic sulfonate is the metal salt of fluorine-containing aliphatic sulfonic, and contains
The metal salt of fluorine aliphatic sulfonic is the alkali metal salt of the fluorine-containing aliphatic sulfonic in molecule comprising at least one C-F key；It is more excellent
Choosing, the metal salt of fluorine-containing aliphatic sulfonic is potassium perfluorobutane sulfonate.
8. fire retardant polycarbonate compositions according to claim 3, it is characterised in that: antioxidant is by quality proportioning
1.0:(0.5-1.0) primary antioxidant and auxiliary anti-oxidant composition；Primary antioxidant and auxiliary anti-oxidant are acrylic ester kind antioxidant, Asia
Phosphoric acid ester antioxidant, the alkylated reaction product of alkylated monophenols or polyphenols and diene, alkylated hydroquinone, hydroxyl
Thiodiphenyl ethers, alkylidenebisphenols, benzyl compounds, β-(3,5- di-t-butyl -4- hydroxy phenyl)-propionic acid and one of base
Ester, the alkylthio of the ester of member or polyalcohol, β-(5- tertiary butyl-4-hydroxy -3- aminomethyl phenyl)-propionic acid and unitary or polyalcohol
Or one or both of amide of the esters of thioaryl compounds, β-(3,5- di-t-butyl -4- hydroxy phenyl)-propionic acid with
On.
9. fire retardant polycarbonate compositions according to claim 3, it is characterised in that: each group including following parts by weight
Point: 96.0-99.8 parts of polycarbonate resin, 0.1-3.0 parts of toughener, 0.01-2.0 parts of fire retardant, 0.01-2.0 parts of antioxidant；
0.05-0.3 parts of lubricant；0.1-0.6 parts of anti-dripping agent；
Wherein, polycarbonate resin is Mitsubishi S-3000F polycarbonate resin, and toughener is the beautiful sun SX-005 of Mitsubishi
Toughener, fire retardant are Mitsubishi EF-42 fire retardant, and anti-hydrolysis agent is German Rhine chemistry Stabaxol P anti-hydrolysis agent,
Antioxidant is by primary antioxidant Chinox 1076 and the 1.0:(0.5-1.0 in mass ratio of auxiliary anti-oxidant THANOX 168) it mixes,
Lubricant is UNISTER-M9676, anti-dripping agent A3800.
10. a kind of method for preparing fire retardant polycarbonate compositions as claimed in any one of claims 1 to 9, feature
It is: the following steps are included:
(1) polycarbonate resin, toughener, fire retardant, anti-hydrolysis agent, antioxidant and other auxiliary agents are weighed respectively by formulation dosage
Afterwards, above-mentioned raw materials are successively put into mixing machine and is blended into uniformly, obtain pre-composition；
(2) it will be prepared in step (1) in resulting pre-composition investment double screw extruder, the screw rod of the double screw extruder is long
Diameter ratio is 40-45:1, and barrel temperature is 250-280 DEG C, screw speed 400-500rpm；The pre-composition is squeezed in the twin-screw
Melting mixing and extruding pelletization in machine out, are made the fire retardant polycarbonate compositions.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021534A (en) * | 2018-07-19 | 2018-12-18 | 中广核俊尔新材料有限公司 | A kind of high-temp resisting high-humidity resisting polycarbonate compositions and preparation method thereof |
| CN110964247A (en) * | 2019-11-21 | 2020-04-07 | 浙江大学宁波理工学院 | Halogen-free flame-retardant reinforced polypropylene and preparation method thereof |
| CN112063148A (en) * | 2020-09-16 | 2020-12-11 | 横店集团得邦工程塑料有限公司 | Hydrolysis-resistant PC composite material with high flame retardant property and preparation method thereof |
| CN112111138A (en) * | 2020-08-25 | 2020-12-22 | 天津金发新材料有限公司 | Flame-retardant polycarbonate composition and preparation method thereof |
| CN112322014A (en) * | 2020-09-29 | 2021-02-05 | 天津金发新材料有限公司 | Low-temperature-resistant PC alloy material and preparation method thereof |
| CN112552668A (en) * | 2020-10-21 | 2021-03-26 | 金发科技股份有限公司 | Long-term stable polycarbonate composition and preparation method thereof |
| CN114149671A (en) * | 2021-11-19 | 2022-03-08 | 天津金发新材料有限公司 | PC/ABS composition and preparation method thereof |
| CN114752200A (en) * | 2022-03-11 | 2022-07-15 | 金发科技股份有限公司 | Wet-heat resistant well-processed PC composition and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381691A (en) * | 2013-07-27 | 2013-11-06 | 乐凯胶片股份有限公司 | Hydrolysis-resistant highly-inflaming-retarding solar cell back film |
| US20150337131A1 (en) * | 2014-05-20 | 2015-11-26 | Konica Minolta, Inc. | Method for producing thermoplastic resin composition |
| CN106916429A (en) * | 2017-03-09 | 2017-07-04 | 江苏金发科技新材料有限公司 | White high tenacity high glowing filament ignition temperature polycarbonate compositions and preparation method thereof |
| CN107556725A (en) * | 2017-08-16 | 2018-01-09 | 上海金发科技发展有限公司 | Halogen-free flame-retardant polycarbonate composition and preparation method thereof |
-
2018
- 2018-11-29 CN CN201811446382.5A patent/CN109535683A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103381691A (en) * | 2013-07-27 | 2013-11-06 | 乐凯胶片股份有限公司 | Hydrolysis-resistant highly-inflaming-retarding solar cell back film |
| US20150337131A1 (en) * | 2014-05-20 | 2015-11-26 | Konica Minolta, Inc. | Method for producing thermoplastic resin composition |
| CN106916429A (en) * | 2017-03-09 | 2017-07-04 | 江苏金发科技新材料有限公司 | White high tenacity high glowing filament ignition temperature polycarbonate compositions and preparation method thereof |
| CN107556725A (en) * | 2017-08-16 | 2018-01-09 | 上海金发科技发展有限公司 | Halogen-free flame-retardant polycarbonate composition and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王文广: "《聚合物改性原理》", 31 March 2018, 中国轻工业出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109021534A (en) * | 2018-07-19 | 2018-12-18 | 中广核俊尔新材料有限公司 | A kind of high-temp resisting high-humidity resisting polycarbonate compositions and preparation method thereof |
| CN109021534B (en) * | 2018-07-19 | 2020-11-10 | 中广核俊尔新材料有限公司 | High-temperature and high-humidity resistant polycarbonate composition and preparation method thereof |
| CN110964247A (en) * | 2019-11-21 | 2020-04-07 | 浙江大学宁波理工学院 | Halogen-free flame-retardant reinforced polypropylene and preparation method thereof |
| CN110964247B (en) * | 2019-11-21 | 2022-08-23 | 浙江大学宁波理工学院 | Halogen-free flame-retardant reinforced polypropylene and preparation method thereof |
| CN112111138A (en) * | 2020-08-25 | 2020-12-22 | 天津金发新材料有限公司 | Flame-retardant polycarbonate composition and preparation method thereof |
| CN112063148A (en) * | 2020-09-16 | 2020-12-11 | 横店集团得邦工程塑料有限公司 | Hydrolysis-resistant PC composite material with high flame retardant property and preparation method thereof |
| CN112322014A (en) * | 2020-09-29 | 2021-02-05 | 天津金发新材料有限公司 | Low-temperature-resistant PC alloy material and preparation method thereof |
| CN112322014B (en) * | 2020-09-29 | 2023-11-17 | 天津金发新材料有限公司 | Low-temperature-resistant PC alloy material and preparation method thereof |
| CN112552668A (en) * | 2020-10-21 | 2021-03-26 | 金发科技股份有限公司 | Long-term stable polycarbonate composition and preparation method thereof |
| CN114149671A (en) * | 2021-11-19 | 2022-03-08 | 天津金发新材料有限公司 | PC/ABS composition and preparation method thereof |
| CN114149671B (en) * | 2021-11-19 | 2023-10-27 | 天津金发新材料有限公司 | PC/ABS composition and preparation method thereof |
| CN114752200A (en) * | 2022-03-11 | 2022-07-15 | 金发科技股份有限公司 | Wet-heat resistant well-processed PC composition and preparation method and application thereof |
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