CN107573667A - High temperature resistant polycarbonate compositions and preparation method thereof - Google Patents
High temperature resistant polycarbonate compositions and preparation method thereof Download PDFInfo
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- CN107573667A CN107573667A CN201710701005.0A CN201710701005A CN107573667A CN 107573667 A CN107573667 A CN 107573667A CN 201710701005 A CN201710701005 A CN 201710701005A CN 107573667 A CN107573667 A CN 107573667A
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Abstract
The invention discloses a kind of high temperature resistant polycarbonate compositions, and it includes PC resin, PET resin, compatilizer, toughener, phosphate ester flame retardants, antioxidant, other auxiliary agents and the calcium constituent based on the polycarbonate compositions gross weight 1.0 60.0ppm.The high temperature resistant polycarbonate compositions are fire retardant using the DBP containing trace TPP, and add 1.0 60.0ppm calcium constituent in said composition kind, the calcium constituent can coordinate with the trace TPP remained in DBP fire retardants, reaction between the suppression PC resin and PET resin of high degree, it can farthest weaken influence of the fire retardant to polycarbonate compositions toughness simultaneously, and the stability of composition color is also improved, the mechanical property and long term color stability of the polycarbonate compositions have great optimization, higher occasion is required especially suitable for high forming temperature and use environment.
Description
Technical field
The present invention relates to a kind of polycarbonate compositions and preparation method thereof, more particularly to a kind of high temperature resistant makrolon group
Compound and preparation method thereof, belong to composite high-molecular technical field.
Background technology
Polycarbonate resin (PC resin) is a kind of unformed thermoplastic of water white transparency, because it is easily worked simultaneously
It is adapted to using a variety of forming methods such as injection, extrusion molding, blowings, and there is preferable mechanics and optical property, therefore extensive use
In many fields such as packaging, commodity, electronic apparatus, toy, instrument, transport and machine manufacture, but pure PC resin is molten
Body viscosity is big, poor solvent resistance and to notch sensitivity is high, cost is also higher.
Pet resin (PET resin) is a kind of thermoplastic polyester of translucent crystal type, is had
The advantages that high-fire resistance, high tenacity, high fatigue durability, self-lubricating, low-friction coefficient, but PET notch impact strength it is low, easily by
Halogenated hydrocarbon corrodes, hydrolytic resistance difference and molding shrinkage are big.There is technical staff that PC resin and PET resin are blended in the prior art
Compound resin is obtained, the compound resin had both had the rigidity and heat resistance of PC resin, had the solvent resistance of PET resin again.
But because PET resin is Crystalline plastics, PC resin is non-Crystalline plastics, PC resin and PET resin
Alloy compatibility is very bad, and both mixing also results in the mechanical property of composite and declined to a great extent.Additionally due to
Contain terminal hydroxy group in PC resin, it at high temperature and has titanium class residual catalyst to deposit with carboxyl, the hydroxyl etc. remained in PET resin
In case, it is very easy that two phase reaction occurs, although reaction can improve compatibility and have greatly uncertainty,
Above-mentioned reaction will also result in the drastically deterioration of composite property during later stage use, substantially reduce PC/PET Alloyapplications
Practicality.Although a small amount of phosphoric acid triphen contained in currently used fire retardant tetraphenyl (bisphenol-A) bisphosphate (BDP)
Ester (TPP) can effectively be complexed titanium class catalyst, but under many circumstances particularly in the case where forming temperature is higher, PC trees
Reaction between fat and PET resin is still more serious, have impact on the popularization and application of PC/PET alloys.
The content of the invention
In order to solve the above technical problems, the invention provides a kind of high temperature resistant polycarbonate compositions and preparation method thereof,
By the preparation method prepare gained polycarbonate compositions toughness is good, colour stability is high, suitable for high forming temperature and right
Use environment requires higher occasion.
The technical scheme is that：
The invention discloses a kind of high temperature resistant polycarbonate compositions, the polycarbonate compositions include it is following by weight
The each component of meter：PC resin 50-85 parts, PET resin 5-20 parts, compatilizer 0.01-5.0 parts, toughener 0.1-13.0 parts, phosphoric acid
Esters fire retardant 8.0-20.0 parts, antioxidant 0.01-2.0 parts, other auxiliary agents 0.01-8.0 parts and based on the polycarbonate composition
Thing gross weight 1.0-60.0ppm calcium constituent.
Wherein PC resin (polycarbonate resin) is to instigate aromatic hydroxy compound to be reacted with phosgene or carbonic diester, or
Aromatic hydroxy compound and a small amount of polyol and phosgene or carbonic diester is set to react the obtained thermoplastic with side chain
Property aromatic polycarbonate polymers or copolymer.The manufacture method of aromatic polycarbonate resin is not particularly limited, and can adopt
With known method, such as phosgenation (interfacial polymerization), fusion method (ester-interchange method).To make formed body outward appearance make moderate progress,
Mobility makes moderate progress, and the molecular weight of polycarbonate resin suitably selects in the present invention, converts what is obtained by solution viscosity
Viscosity average molecular weigh [Mv] is usually more than 10000, preferably more than 12000, and usually less than 40000, preferably 30000 with
Under, more preferably less than 25000.By the way that viscosity average molecular weigh is set in aforementioned range, it is ensured that poly- carbonic acid of the invention
The mechanical strength of ester resin composition, it is more preferable at the field higher for requirement of mechanical strength.
Wherein PET resin is inherent viscosity 0.5-0.9dl/g primary PET resin, or passes through separation, cleaning, crushes, again
Regenerative PET resin made from extruding pelletization after cleaning, drying, the inherent viscosity of the regenerative PET resin is also 0.5-0.9dl/g.
Wherein compatilizer is Methylacrylate-Acrylate Copolymer, atactic styrene-maleic anhydride copolymer and benzene
At least one of ethylene-propylene nitrile-GMA, preferably styrene-acrylonitrile-methacrylic acid contracting
Water glyceride.
Wherein toughener is MBS, methyl methacrylate-acrylic acid
Copolymer, ethylene-methyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-acrylate-methacrylic acid contracting
Water glyceride terpolymer, the ethylene-vinyl acetate copolymer of maleic anhydride functional, acrylic compounds toughener and organosilicon
At least one of rubber graft toughener, preferably organic silicon rubber graft toughener.The organic silicon rubber graft
Toughener refers to the copolymer formed containing polysiloxane and ethene polymers rubber with grafting vinyl monomer, wherein rubber
Volume average particle size be 200-2000nm, preferably 220-1500nm, more preferably 280-1000nm, still more preferably for
290-600nm, by making the volume average particle size of rubber in the range of 290-600nm, it can obtain preferable impact resistance and to rising
Firing temperature influences small resin combination.
Wherein phosphate ester flame retardants are the fire retardants based on tetraphenyl (bisphenol-A) bisphosphate (DBP), and the DBP
In also include trace Triphenyl phosphate (TPP), from conventional use of DBP fire retardants on the market, this kind in the present invention
The TPP of trace is generally remained in fire retardant, the Specific amounts of the trace is what be left behind in DBP fire retardant production processes, is
It is well-known to those skilled in the art, repeated no more in the application.
Wherein calcium constituent can by polycarbonate compositions process of manufacture directly thereto add calcium simple substance or
Calcium containing compound realizes that above-mentioned calcium containing compound is calcium sulfate, calcium chloride, calcium nitrate, calcium carbonate, calcium phosphate and calcic network
At least one of compound.The addition of the calcium simple substance and calcium containing compound is to make calcium constituent in the polycarbonate compositions
Content reaches 1.0-60.0ppm, preferably 6.0-20.0ppm.
Wherein antioxidant can be propionic acid ester antioxidant, such as octadecyl -3- (3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic ester；Organic phosphites antioxidant, such as three (nonyl phenyl) phosphite esters, double (2,4- di-tert-butyl-phenyl) seasons
Penta tetrol diphosphites, distearyl pentaerythrityl diphosphite；The monophenols or polyphenols kind antioxidant of alkylation；Polyphenol with
The reaction product kind antioxidant of the alkylation of diene, such as four [methylene (3,5- di-t-butyl -4- hydroxy hydrocinnamates)]
Methane；The butylated reaction product of paracresol or bicyclopentadiene is as antioxidant；The hydroquinones of alkylation is as antioxygen
Agent；Hydroxylated thiodiphenyl ethers are as antioxidant；Alkylidenebisphenols are as antioxidant；Benzyl compounds are as antioxidant；β-
(3,5- di-t-butyl -4- hydroxy phenyls)-propionic acid is with the ester of unitary or polyalcohol as antioxidant；β-(the 5- tert-butyl group -4- hydroxyls
Base -3- aminomethyl phenyls)-propionic acid and unitary or polyalcohol ester as antioxidant；The ester of alkylthio or thioaryl compounds
As antioxidant, such as distearyl thiopropionate, dilauryl thiopropionate, tricosyl thiodipropionate, season
[3- (the 3,5- di-t-butyl 4- hydroxy phenyls) propionic ester of penta 4 alcohol radical-four；β-(3,5- di-t-butyl -4- hydroxy phenyls)-the third
The acid amides of acid is as antioxidant, or includes the combination of at least one of above-mentioned antioxidant.
Other auxiliary agents such as anti-dripping agent, plasticizer, filler, colouring agent can also be properly added as needed in this application
At least one of.Anti-dripping agent is preferably fluorinated polyolefin, specifically may include fluoride resin, TFE, four
PVF/hexafluoropropylene copolymer resin, wherein it is preferred that TFE.Lubricant is tristerin；Filler includes
The mineral fillers such as titanium dioxide, barium sulfate；Colouring agent includes various pigment, dyestuff.
Present invention also offers a kind of preparation method of above-mentioned high temperature resistant polycarbonate compositions, under the preparation method includes
State step：It will be blended into uniformly in each raw material input mixer that gained is weighed by formula dosage, obtain pre-composition；Then should
Pre-composition input double screw extruder melting mixing and extruding pelletization, obtain the high temperature resistant polycarbonate compositions；It is wherein double
The screw slenderness ratio example of screw extruder is (40-45):1, barrel temperature is 240-260 DEG C, screw speed 400-500rpm.
The method have the benefit that：The high temperature resistant polycarbonate compositions are resistance using the DBP containing trace TPP
Agent is fired, and can be with the trace that is remained in DBP fire retardants in said composition kind addition 1.0-60.0ppm calcium constituent, the calcium constituent
Measure TPP to coordinate, the reaction between the suppression PC resin and PET resin of high degree, while can farthest weaken fire retardant
Influence to polycarbonate compositions toughness, and the stability of composition color is also improved, the polycarbonate compositions
Mechanical property and long term color stability have great optimization, compare especially suitable for high forming temperature and use environment requirement
High occasion.
Embodiment
In order to better understand the technological means of the present invention, and can be practiced according to the content of specification, below
In conjunction with specific embodiments, the embodiment of the present invention is described in further detail, following examples are used to illustrate this hair
It is bright, but it is not limited to the scope of the present invention.
Each raw material used in following specific embodiments and comparative example are as described below：
PC resin：Viscosity average molecular weigh is 20000, and trade mark S-3000F, producer is Mitsubishi.
PET resin：Inherent viscosity is 0.68dl/g, and the trade mark is PET SB500, and producer is Yizheng petrochemical industry.
Compatilizer：Styrene-acrylonitrile-GMA, trade mark SAG-002, producer are Nantong day
Liter.
Toughener：S-2001, producer are the beautiful sun of Mitsubishi.
Fire retardant：PhireGuard BDP, producer are refined gram of Jiangsu.
Antioxidant：Chinox 1076；Producer is TaiWan, China double bond chemical industry.
Lubricant：UNISTER-M9676, producer are Japan Oil Co.
Anti-dripping agent：The trade mark is A3800, and producer is the beautiful sun of Mitsubishi.
Calcic simple substance or calcium containing compound：Calcium phosphate, calcium carbonate, it is commercially available gained.
Each raw material is weighed according to dosage is formulated described in table 1 below and table 2, each raw material for weighing gained is put into mixer
In be blended into uniformly, obtain pre-composition；Then the pre-composition is put into double screw extruder melting mixing and extruding pelletization, obtained
Polycarbonate compositions described herein；Wherein the screw slenderness ratio example of double screw extruder is 40:1, barrel temperature is
240-260 DEG C, screw speed 400-500rpm.
The specific embodiment 1-8 each component dosage (units of table 1：kg)
The comparative example 1-4 each component dosage (units of table 2：kg)
Polycarbonate compositions obtained by above-mentioned preparation are subjected to calcium element content measure, notched Chalpy impact intensity is surveyed
Fixed and colour stability measure, its assay method or bioassay standard are as described below：
(1) calcium element content determines：The particle 2g of accurate weighing polycarbonate compositions, is poured into assay balance
In 100ml resolution bottle, 97wt.% concentrated sulfuric acid 5ml is then added, in the iron plate heating instrument that preset temperature is 300 DEG C
10min is heated, then adds 68wt.% nitric acid 5ml, then keeps heating 20min, particulate matter is cooled to after decomposing completely
Room temperature, add in 20ml hydrogen peroxide and it is acid be 7 to pH value after, dilute aforesaid liquid with deionized water, liquid passed through into sample introduction
Pipe imports in ICP detecting instruments the concentration for determining calcium constituent.
(2) notched Chalpy impact intensity determines：Under the conditions of 23 DEG C, rushed using molding notched izod thick 3.2mm
Rod measure notched Chalpy impact intensity is hit, notched Chalpy impact intensity is determined according to ASTM D256, result is recorded with J/m.
(3) colour stability determines：The 80 tons of injection (mo(u)lding) machines manufactured using Nissei Plastic Industrial Co., Ltd, in barrel
Temperature is to be detained 0 and 20min respectively at 300 DEG C, is then molded the polycarbonate compositions in the present invention, produces thickness
2 millimeters of degree, 40 millimeters of width, the plate of 100 millimeters of length, wherein for mold temperature set at 80 DEG C, injection molding plates are wet in 23 DEG C of room temperature
After the regulation of degree 50% 48h, using Ai Seli Color Eye 7000A, with D65After light source bounce technique is to heat retention 0 and 20min
The tone (L, a, b) of profiled sheeting be measured, aberration Δ E is obtained by following formula, as a result shown：Δ E is bigger, and shaping color is steady
It is qualitative poorer.Δ E={ (L-L ')2+(a-a’)2+(b-b’)2}1/2。
Above-mentioned test result is referring to shown in table 3 and table 4.
The specific embodiment 1-8 performance measurement results of table 3
The comparative example 1-4 performance measurement results of table 4
As can be seen that embodiment 1-8 and comparative example 1-4 prepares the polycarbonate compositions of gained from above-mentioned table 3 and table 4
Compare, the aberration after the notched impact properties of the polycarbonate compositions obtained by comparative example 1-4 or heat retention have or it is high or
Low variation, it is impossible to meet the use condition that some are required to toughness and condition of molding is harsh.Different from comparative example 1-4, sheet
Polycarbonate compositions obtained by inventive embodiments coordinate after it with the addition of calcium constituent with the TPP remained in fire retardant, can pole
Reaction between the suppression PC resin and PET resin of big degree, while can farthest weaken fire retardant to composition toughness
Influence, colour stability is also improved after composition heat retention in addition.
High performance 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, the part manufacture material etc. of automotive material and other industrial circles.
Above example is used for illustrative purposes only, rather than limitation of the present invention, the technology people about technical field
Member, without departing from the spirit and scope of the present invention, can also make various conversion or modification, therefore all equivalent
Technical scheme should also belong to scope of the invention, should be limited by each claim.
Claims (10)
- A kind of 1. high temperature resistant polycarbonate compositions, it is characterised in that：Including following each components by weight：PC resin 50-85 parts, PET resin 5-20 parts, compatilizer 0.01-5.0 parts, toughener 0.1-13.0 parts, phosphate ester flame retardants 8.0- 20.0 parts, antioxidant 0.01-2.0 parts, other auxiliary agents 0.01-8.0 parts and based on polycarbonate compositions gross weight 1.0- 60.0ppm calcium constituent.
- 2. high temperature resistant polycarbonate compositions according to claim 1, it is characterised in that：The dosage of the calcium constituent is base In the 6.0-20.0ppm of the polycarbonate compositions gross weight.
- 3. high temperature resistant polycarbonate compositions according to claim 2, it is characterised in that：The calcium constituent derives from calcium list Matter or calcium containing compound.
- 4. high temperature resistant polycarbonate compositions according to claim 3, it is characterised in that：The calcium containing compound is sulfuric acid Calcium, calcium chloride, calcium nitrate, calcium carbonate, calcium phosphate and containing at least one of calcium complex.
- 5. high temperature resistant polycarbonate compositions according to claim 1, it is characterised in that：The phosphate ester flame retardants with Based on tetraphenyl (bisphenol-A) bisphosphate, and also include trace Triphenyl phosphate in the phosphate ester flame retardants.
- 6. high temperature resistant polycarbonate compositions according to claim 1, it is characterised in that：The PC resin is to glue equal molecule Measure at least one of 10000-40000 aromatic copolycarbonate；The PET resin is inherent viscosity 0.5-0.9dl/g's Primary PET resin or regenerative PET resin.
- 7. high temperature resistant polycarbonate compositions according to claim 1, it is characterised in that：The compatilizer is metering system Acid esters-acrylate copolymer, atactic styrene-maleic anhydride copolymer and styrene-acrylonitrile-Glycidyl methacrylate are sweet At least one of grease.
- 8. high temperature resistant polycarbonate compositions according to claim 1, it is characterised in that：The toughener is metering system Sour methyl esters-BS, methyl methacrylate-acrylic acid copolymer, ethylene-methyl acrylate copolymer, Ethylene-butyl acrylate copolymer, ethylene-acrylate-GMA terpolymer, maleic anhydride work( At least one of ethylene-vinyl acetate copolymer, acrylic compounds toughener and organic silicon rubber graft toughener of energyization.
- 9. high temperature resistant polycarbonate compositions according to claim 1, it is characterised in that：The toughener is organosilicon rubber Glue graft toughener, and wherein the volume average particle size of rubber is 200-2000nm.
- 10. a kind of preparation method of the high temperature resistant polycarbonate compositions in claim 1 to 9 described in any claim, its It is characterised by：Comprise the steps：It will be blended into uniformly, obtain in each raw material input mixer that gained is weighed by formula dosage Pre-composition；Then the pre-composition is put into double screw extruder melting mixing and extruding pelletization, obtains the poly- carbonic acid of the high temperature resistant Ester composition；Wherein the screw slenderness ratio example of double screw extruder is (40-45):1, barrel temperature is 240-260 DEG C, and screw rod turns Speed is 400-500rpm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625403A (en) * | 2020-12-16 | 2021-04-09 | 江苏吉福新材料股份有限公司 | High-heat-resistance resin and preparation method and application thereof |
| CN115651387A (en) * | 2022-11-11 | 2023-01-31 | 万华化学（宁波）有限公司 | Polycarbonate composition capable of being stably produced and preparation method thereof |
| CN115948040A (en) * | 2022-09-30 | 2023-04-11 | 江苏金发科技新材料有限公司 | Polycarbonate composition and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565538A (en) * | 2008-04-22 | 2009-10-28 | 金发科技股份有限公司 | Halogen free flame retardant PC/polyester alloy and preparation method thereof |
| CN104987691A (en) * | 2015-06-09 | 2015-10-21 | 金发科技股份有限公司 | Polycarbonate composition and preparation method thereof |
-
2017
- 2017-08-16 CN CN201710701005.0A patent/CN107573667B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565538A (en) * | 2008-04-22 | 2009-10-28 | 金发科技股份有限公司 | Halogen free flame retardant PC/polyester alloy and preparation method thereof |
| CN104987691A (en) * | 2015-06-09 | 2015-10-21 | 金发科技股份有限公司 | Polycarbonate composition and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625403A (en) * | 2020-12-16 | 2021-04-09 | 江苏吉福新材料股份有限公司 | High-heat-resistance resin and preparation method and application thereof |
| CN115948040A (en) * | 2022-09-30 | 2023-04-11 | 江苏金发科技新材料有限公司 | Polycarbonate composition and preparation and application thereof |
| CN115948040B (en) * | 2022-09-30 | 2024-04-16 | 江苏金发科技新材料有限公司 | Polycarbonate composition and preparation and application thereof |
| CN115651387A (en) * | 2022-11-11 | 2023-01-31 | 万华化学（宁波）有限公司 | Polycarbonate composition capable of being stably produced and preparation method thereof |
| CN115651387B (en) * | 2022-11-11 | 2023-08-11 | 万华化学（宁波）有限公司 | Polycarbonate composition capable of being stably produced and preparation method thereof |
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