CN101974216A - Halogen-free flame-retardant PC/ABS alloy - Google Patents
Halogen-free flame-retardant PC/ABS alloy Download PDFInfo
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- CN101974216A CN101974216A CN2010105242259A CN201010524225A CN101974216A CN 101974216 A CN101974216 A CN 101974216A CN 2010105242259 A CN2010105242259 A CN 2010105242259A CN 201010524225 A CN201010524225 A CN 201010524225A CN 101974216 A CN101974216 A CN 101974216A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
The invention provides a halogen-free flame-retardant PC/ABS alloy. In the invention, by adopting a double screw extruder the middle part of which is provided with a lateral feed inlet, firstly PC, ABS and other masterbatches as well as a compatilizer are added to the extruder based on measurement via a hopper at a feed end of the extruder for melting and blending, addictives such as a flame retardant, an inorganic nano-filler and the like are added to the extruder based on measurement via the lateral feed inlet, and then the addictives are mixed with the melted PC, ABS and other masterbatches for extrusion and granulation. In the processing course of the halogen-free flame-retardant PC/ABS alloy, the halogen-free flame retardant and other addictives are added to the double screw extruder in a lateral feed manner and mixed with the masterbatches for processing, thus reducing retention time of the flame retardant and other components in the extruder, and avoiding degradation of the flame retardant during processing; in addition, PC granules and PC powder are selected as raw materials, thus obviously improving the blending property of PC and ABS. The halogen-free flame-retardant PC/ABS alloy of the invention has the advantages of low production cost, good processing properties, high flame-retardant level and environmental protection.
Description
Technical field
The present invention relates to a kind of high polymer alloy, be specifically related to a kind of halogen-free flame retardant PC/ABS alloy.
Background technology
PC/ABS is a kind of alloy material that is formed by PC (polycarbonate) and ABS (acrylonitrile-butadiene-styrene copolymer) blend according to a certain percentage.Wherein PC is a kind of armorphous thermoplastic resin of high comprehensive performance, have excellent electrical insulating property, extensibility, dimensional stability and chemical resistance, higher intensity, thermotolerance and winter hardiness, also have from put out, advantage such as fire-retardant, nontoxic, pigmentable, but also there is not anti-strong acid in PC, not anti-highly basic, not UV resistant, and processing difficulties, the goods unrelieved stress is big, easy stress cracking, to shortcomings such as breach sensitivities, this has restricted it in industrial development and application.And ABS resin is a kind of intensity height, good toughness, is easy to the thermoplastic macromolecule material of machine-shaping.
The PC/ABS alloy is the premium properties of PC and ABS comprehensively, improves resistance toheat, shock resistance and the tensile strength of ABS, reduces PC cost and melt viscosity, improves processing characteristics, reduces goods internal stress and the heavy machine gun susceptibility for products thickness.This PC/ABS alloy material can be widely used on internals, business machine, the communication apparatus, electrical home appliances and the set lights of automobile.
In recent years, in order to satisfy the particular requirement of material at Application Areas (particularly electronic and electrical equipment) fire safety, the PC/ABS alloy must be with excellent flame-retardant, and therefore, the flame-retarded technology of PC/ABS alloy becomes the focus of people's research.And along with people are more and more higher for environmental protection and safe requirement cry, also more and more higher to the requirement of material environment friendly.So people turn to the Non-halogen Flame Retardant Technology field gradually for the research emphasis of fire retardant material.The preparation of halogen-free flame retardant PC/ABS alloy is all disclosed as Chinese patent 200910191931,200410051776, CN 02115265,200910024721,200810239020 etc., but still there is certain defective in the above patent, loaded down with trivial details as some preparation method's preparation process, repeatedly use forcing machine etc., improved manufacturing cost, and fire retardant high temperature degradation occurs after handling through multiple high temp easily, causes problems such as the mechanical property of alloy material and flame retardant properties reduction.
Summary of the invention
The present invention is intended to overcome the deficiencies in the prior art, provides that a kind of production cost is low, mechanical strength is high, the halogen-free flame retardant PC/ABS alloy of good flame retardation effect, processing characteristics excellence.
For solving above technical problem, the technical scheme that the present invention takes is:
A kind of halogen-free flame retardant PC/ABS alloy, in weight part, described halogen-free flame retardant PC/ABS alloy materials comprises:
Polycarbonate pellet 30-40 part;
Polycarbonate powder 30-40 part;
ABS resin 10-35 part;
Styrene-acrylonitrile copolymer 5-15 part;
Polystyrene maleic anhydride graft copolymer 4-8 part;
Phosphoric acid ester organism fire retardant 4-10 part;
Polytetrafluoroethylene powder 0.3-1.2 part;
Nanometer inorganic filler 0.5-1.0 part;
Oxidation inhibitor 0.1-0.5 part;
Photostabilizer 0.1-0.2 part;
Described halogen-free flame retardant PC/ABS alloy is extruded by screw extrusion press by above-mentioned raw materials and is processed to form;
Described screw extrusion press has first opening for feed and the discharge port that lays respectively at two ends, second opening for feed of the described first opening for feed 1/3-2/3 screw extrusion press length of distance between described first opening for feed and discharge port, when extruding, ABS resin, styrene-acrylonitrile copolymer, polycarbonate pellet, the polycarbonate powder, the polystyrene maleic anhydride graft copolymer is fed in the screw extrusion press by first opening for feed, phosphoric acid ester organism fire retardant, polytetrafluoroethylene powder, nanometer inorganic filler, oxidation inhibitor and photostabilizer feed the screw extrusion press from described second opening for feed.
According to the present invention, described polystyrene maleic anhydride graft copolymer PS-g-MAH is a compatilizer, can improve the consistency that PC and ABS add man-hour; Described phosphoric acid ester organism fire retardant is two (diphenyl phosphate) RDP of Resorcinol or dihydroxyphenyl propane-two (diphenyl phosphate) BDP; Described nanometer inorganic filler is nano-calcium carbonate, silicon oxide etc.; Described oxidation inhibitor is Hinered phenols or phosphite ester kind antioxidant, is specially antioxidant 1010 or oxidation inhibitor 168; Described photostabilizer is the hindered amines stablizer.
According to the present invention, described polytetrafluoroethylene powder is an Antidrip agent, and its effect is to prevent or to reduce incendiary molten drop drippage when material combustion, in case cause other material combustion.
According to the present invention, the number-average molecular weight of employed polycarbonate pellet is the common process pellet between 24000-30000, and particle diameter is generally between 1.5 millimeters～5 millimeters.The number-average molecular weight of described polycarbonate powder is between 30000-35000, and granularity is between 200 orders～1500 orders; Using the mixture of PC pellet and PC powder is in order to improve the processing characteristics of PC, especially PC and the ABS resin blended characteristic in melt extruding process as the PC masterbatch.
According to the present invention, extrude and add man-hour, described screw extrusion press is divided into six temperature ranges successively from first opening for feed to discharge port, and the temperature of six temperature ranges is respectively: a district temperature 195-210 ℃, two district temperature 211-225 ℃, three district temperature 226-240 ℃, four district temperature 241-250 ℃, five district temperature 225-240 ℃, six district temperature 210-224 ℃;
Described second opening for feed directly communicates with four districts.
PC/ABS alloy of the present invention, the mixture of selecting PC pellet and PC powder for use can obviously improve the processing characteristics of PC and ABS as the PC masterbatch; In the extrusion process, the form of additives such as fire retardant with the side direction feeding added in the screw extrusion press by second opening for feed, with plastifying masterbatch blend, once finish extrusion process, the high temperature degradation problem that when saving processing step, can avoid additive such as fire retardant to cause because of overstand at high temperature; The prepared PC/ABS alloy production of the present invention cost is low, and flame retardant properties is good, also has better mechanical property and over-all properties, can be applied in automotive industry and the electric industry.
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment, but be not limited to these embodiment.
The prepared halogen-free flame retardant PC of the present invention/ABS alloy material adopts following method or standard to carry out performance test, and all test bars need be deposited under humidity 50% ± 5% condition and be not less than 16 hours in temperature 23 ℃ ± 2:
Tensile strength: test according to standard A STM D638;
Elongation at break: test according to standard A STM D638;
Flexural strength: test according to standard A STM D790;
Modulus in flexure: test according to standard A STM D790;
Notched Izod impact strength: test according to standard A STM D256;
Heat-drawn wire: test test condition load 18.6kg according to standard A STM D648;
Flame retardant resistance: test according to standard UL 94;
Melting index: test according to standard A STM D1238, test condition is 260 ℃, 5kg load.
Embodiment and Comparative Examples 1:
The used forcing machine of this example is a twin screw extruder, and described twin screw extruder has first opening for feed and the discharge port that lays respectively at two ends, second opening for feed that is positioned at described first opening for feed and discharge port middle part.
According to parts by weight, the dry 12h under 80 ℃ of conditions with ABS resin and AS resin (styrene-acrylonitrile copolymer); With PC (polycarbonate) pellet dry 10h under 100 ℃ of conditions, PC (polycarbonate) powder dry 4h under 100 ℃ of conditions; Above dried material and compatilizer PS-g-MAH (polystyrene maleic anhydride graft copolymer) are added in the high-speed mixer, under 1000～5000 rev/mins rotating speed, mix.Join the twin screw extruder through first opening for feed of metering then from described twin screw extruder.Simultaneously additives such as fire retardant RDP and BDP, polytetrafluoroethylene powder, nanometer inorganic filler, antioxidant 1010, antioxidant 168 and photostabilizer are carried out low speed mixing, join the middle part of twin screw extruder from second opening for feed of described twin screw extruder with the form of side direction feeding after metering, with melt-mixing extruding pelletizations such as plastifying PC, ABS, AS and PS-g-MAH.The extrusion temperature of used twin screw extruder is: district's temperature: 205 ℃, two district's temperature: 215 ℃, three district's temperature: 230 ℃, four district's temperature: 240 ℃, five district's temperature: 230 ℃, six district's temperature: 220 ℃, the twin screw rotating speed is 300 rev/mins.Obtain halogen-free flame retardant PC/ABS alloy.
Comparative Examples 2:
This routine used forcing machine is the common double screw extrusion press.
According to parts by weight, the dry 12h under 80 ℃ of conditions with ABS resin and AS resin; With PC pellet dry 10h under 100 ℃ of conditions, the PC powder is dry 4h under 100 ℃ of conditions; Above dried material is added in the high-speed mixer with compatilizer PS-g-MAH, fire retardant RDP and BDP, polytetrafluoroethylene powder, nanometer inorganic filler, antioxidant 1010, antioxidant 168 and photostabilizer etc., under 1000～5000 rev/mins rotating speed, mix.Then through being metered into extruding pelletization in the twin screw extruder.The extrusion temperature of used twin screw extruder is: district's temperature: 205 ℃, two district's temperature: 215 ℃, three district's temperature: 230 ℃, four district's temperature: 240 ℃, five district's temperature: 230 ℃, six district's temperature: 220 ℃, the twin screw rotating speed is 300 rev/mins, and the residence time is 1-3 minute.Obtain halogen-free flame retardant PC/ABS alloy.
The composition of raw materials of each embodiment and Comparative Examples sees Table 1;
The performance of the prepared PC/ABS alloy of each embodiment and Comparative Examples sees Table 2.
By table 2 as seen, the every performance of material that embodiment and Comparative Examples 1 are processed gained with additives such as fire retardants with side direction feeding form all is better than Comparative Examples 2 with common process mode gained material, especially combustionproperty, embodiment and Comparative Examples 1 gained material all reach the V-0 rank, and 2 of Comparative Examples reach the V-1 rank.The fire-retardant rank height of PC/ABS alloy that the present invention is prepared, excellent combination property and toxic substance such as not halogen-containing especially can satisfy the demand of electric industry to macromolecular material.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; can not limit protection scope of the present invention with this; all equivalences of doing according to spirit of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
The prescription of each embodiment of table 1 and Comparative Examples
| Prescription | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 |
| The PC pellet | 40 | 30 | 40 | 40 | 70 | 40 |
| The PC powder | 30 | 40 | 30 | 40 | 0 | 30 |
| ABS | 15 | 15 | 25 | 25 | 15 | 15 |
| AS | 15 | 15 | 5 | 10 | 15 | 15 |
| Compatilizer | 8 | 8 | 8 | 7 | 8 | 8 |
| Fire retardant BDP | 5 | 5 | 5 | 5 | 5 | 5 |
| Fire retardant RDP | 5 | 5 | 5 | 3 | 5 | 5 |
| Polytetrafluoroethylene powder | 0.4 | 0.4 | 0.4 | 0.6 | 0.4 | 0.4 |
| Nanometer inorganic filler | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Antioxidant 1010 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Antioxidant 168 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| The HAL photostabilizer | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
The performance comparison of each embodiment of table 2 and Comparative Examples gained PC/ABS alloy
Claims (8)
1. halogen-free flame retardant PC/ABS alloy, it is characterized in that: in weight part, described halogen-free flame retardant PC/ABS alloy materials comprises:
Polycarbonate pellet 30-40 part;
Polycarbonate powder 30-40 part;
ABS resin 10-35 part;
Styrene-acrylonitrile copolymer 5-15 part;
Polystyrene maleic anhydride graft copolymer 4-8 part;
Phosphoric acid ester organic fire-retardant 4-10 part;
Polytetrafluoroethylene powder 0.3-1.2 part;
Nanometer inorganic filler 0.5-1.0 part;
Oxidation inhibitor 0.1-0.5 part;
Photostabilizer 0.1-0.2 part;
Described halogen-free flame retardant PC/ABS alloy is extruded by screw extrusion press by above-mentioned raw materials and is processed to form;
Described screw extrusion press has first opening for feed and the discharge port that lays respectively at two ends, second opening for feed of the described first opening for feed 1/3-2/3 screw extrusion press length of distance between described first opening for feed and discharge port, when extruding, ABS resin, styrene-acrylonitrile copolymer, polycarbonate pellet, the polycarbonate powder, the polystyrene maleic anhydride graft copolymer is fed in the screw extrusion press by first opening for feed, phosphoric acid ester organism fire retardant, polytetrafluoroethylene powder, nanometer inorganic filler, oxidation inhibitor and photostabilizer feed the screw extrusion press from described second opening for feed.
2. halogen-free flame retardant PC according to claim 1/ABS alloy is characterized in that: described phosphoric acid ester organism fire retardant is two (diphenyl phosphate) or dihydroxyphenyl propane-two (diphenyl phosphates) of Resorcinol.
3. halogen-free flame retardant PC according to claim 1/ABS alloy is characterized in that: described oxidation inhibitor is Hinered phenols or phosphite ester kind antioxidant.
4. according to claim 1 or 3 described halogen-free flame retardant PC/ABS alloys, it is characterized in that: described oxidation inhibitor is antioxidant 1010 or oxidation inhibitor 168.
5. halogen-free flame retardant PC according to claim 1/ABS alloy is characterized in that: described photostabilizer is the hindered amines stablizer.
6. halogen-free flame retardant PC according to claim 1/ABS alloy is characterized in that, the number-average molecular weight of polycarbonate pellet is 24000-30000, and particle diameter is between 1.5 millimeters～5 millimeters; The number-average molecular weight of polycarbonate powder is 30000-35000, and granularity is between 200 orders～1200 orders.
7. halogen-free flame retardant PC according to claim 1/ABS alloy is characterized in that: described second opening for feed is positioned at the middle part of described screw extrusion press.
8. halogen-free flame retardant PC according to claim 1/ABS alloy, it is characterized in that: described twin screw extruder is divided into six temperature ranges successively from first opening for feed to discharge port, and the temperature of six temperature ranges is respectively: a district temperature 195-210 ℃, two district temperature 211-225 ℃, three district temperature 226-240 ℃, four district temperature 241-250 ℃, five district temperature 225-240 ℃, six district temperature 210-224 ℃;
Described second opening for feed directly communicates with four districts.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146202A (en) * | 2011-04-20 | 2011-08-10 | 上海锦湖日丽塑料有限公司 | Flame-retardant PC (polycarbonate) /ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) alloy for screw hole cracking resistance experiment and preparation method thereof |
| CN102181142A (en) * | 2011-04-22 | 2011-09-14 | 浙江杭海塑业有限公司 | Halogen-free flame-retardant high-toughness modified polycarbonate |
| CN102181141A (en) * | 2011-04-22 | 2011-09-14 | 浙江杭海塑业有限公司 | Preparation method of halogen-free flame-retardant and high-toughness modified polycarbonate (PC) |
| CN102344661A (en) * | 2011-10-26 | 2012-02-08 | 惠州市沃特新材料有限公司 | PC (Polycarbonate)/ABC (Acrylonitrile-Butadiene-Styrene copolymer) engineering plastics, as well as preparation method and application thereof |
| CN102888086A (en) * | 2011-07-22 | 2013-01-23 | 纳幕尔杜邦公司 | Flame-retardant composition having improved melt liquidity |
| CN109320935A (en) * | 2018-08-30 | 2019-02-12 | 江苏金发科技新材料有限公司 | Improve the production technology of Polycarbonate alloy material toner point |
| CN109679313A (en) * | 2018-12-17 | 2019-04-26 | 上海凯雄新材料科技有限公司 | A kind of PC-ABS plastic building template that can be recycled |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101418118A (en) * | 2008-12-05 | 2009-04-29 | 北京化工大学 | Halogen-free flame retardant PC/ABS alloy and preparation method thereof |
| CN101445653A (en) * | 2008-12-11 | 2009-06-03 | 上海交通大学 | Preparation method of non-halogen flame-retarded makrolan/acrylonitrile-butadiene-styrene copolymer alloy |
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2010
- 2010-10-29 CN CN2010105242259A patent/CN101974216B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418118A (en) * | 2008-12-05 | 2009-04-29 | 北京化工大学 | Halogen-free flame retardant PC/ABS alloy and preparation method thereof |
| CN101445653A (en) * | 2008-12-11 | 2009-06-03 | 上海交通大学 | Preparation method of non-halogen flame-retarded makrolan/acrylonitrile-butadiene-styrene copolymer alloy |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146202A (en) * | 2011-04-20 | 2011-08-10 | 上海锦湖日丽塑料有限公司 | Flame-retardant PC (polycarbonate) /ABS (Acrylonitrile Butadiene StyreneAcrylonitrile Butadiene Styrene) alloy for screw hole cracking resistance experiment and preparation method thereof |
| CN102181142A (en) * | 2011-04-22 | 2011-09-14 | 浙江杭海塑业有限公司 | Halogen-free flame-retardant high-toughness modified polycarbonate |
| CN102181141A (en) * | 2011-04-22 | 2011-09-14 | 浙江杭海塑业有限公司 | Preparation method of halogen-free flame-retardant and high-toughness modified polycarbonate (PC) |
| CN102888086A (en) * | 2011-07-22 | 2013-01-23 | 纳幕尔杜邦公司 | Flame-retardant composition having improved melt liquidity |
| CN102344661A (en) * | 2011-10-26 | 2012-02-08 | 惠州市沃特新材料有限公司 | PC (Polycarbonate)/ABC (Acrylonitrile-Butadiene-Styrene copolymer) engineering plastics, as well as preparation method and application thereof |
| CN109320935A (en) * | 2018-08-30 | 2019-02-12 | 江苏金发科技新材料有限公司 | Improve the production technology of Polycarbonate alloy material toner point |
| CN109320935B (en) * | 2018-08-30 | 2021-01-05 | 江苏金发科技新材料有限公司 | Production process for improving polycarbonate alloy material color powder point |
| CN109679313A (en) * | 2018-12-17 | 2019-04-26 | 上海凯雄新材料科技有限公司 | A kind of PC-ABS plastic building template that can be recycled |
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