CN102936403A - Halogen-free flame-retardant polycarbonate composition and preparation method thereof - Google Patents
Halogen-free flame-retardant polycarbonate composition and preparation method thereof Download PDFInfo
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- CN102936403A CN102936403A CN2011102334569A CN201110233456A CN102936403A CN 102936403 A CN102936403 A CN 102936403A CN 2011102334569 A CN2011102334569 A CN 2011102334569A CN 201110233456 A CN201110233456 A CN 201110233456A CN 102936403 A CN102936403 A CN 102936403A
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Abstract
The invention discloses a halogen-free flame-retardant polycarbonate composition, which comprises the following components by weight: 30-50 parts of polycarbonate; 20-45 parts of polylactic acid; 15-30 parts of a flame-retardant masterbatch; 0.5-1 part of an antidrip additive; 2-5 parts of a filling modification agent; and 5-10 parts of a compatilizer. The product provided in the invention has excellent flame retardance, and maintains good mechanical properties and other characteristics at the same time, thus being able to meet the use requirements of electronic communication equipment shells, automobile internal structure components and other products. The flame-retardant masterbatch adopted by the halogen-free flame-retardant polycarbonate composition provided in the invention has good compatibility, and twin-screw extrusion equipment is employed. The polycarbonate composition has the advantages of simple and continuous process, high production efficiency, as well as stable product quality.
Description
Technical field
The present invention relates to a kind of halogen-free and flame-retardant polycarbonate mixture and preparation method thereof.Particularly interpolation has the poly(lactic acid) of biological degradation function in polycarbonate resin, on the basis that keeps material good mechanical properties, thermostability, chemical stability and processing characteristics, polycarbonate is realized the effect of environmental protection flame retardant.
Background technology
Polycarbonate (PC) is applied in a lot of fields owing to have high strength, high tenacity, high heat resistance, the transparency.In addition according to variant production performance or production cost requirement, polycarbonate can with other resins, for example ABS resin, polystyrene resin, nylon etc. mix use, with thickness dependence of existing in the moulding processability that improves polycarbonate, the shock-resistance etc., thereby be applied to the field such as shell, automotive interior component of electronic communication equipment.
Poly(lactic acid) (PLA) is a kind of novel biodegradable material, and the starch material that uses reproducible plant resources (such as corn) to propose is made.Starch material is made lactic acid via fermenting process, converts poly(lactic acid) to by chemosynthesis again, and raw material sources are very abundant.It has good biodegradability, can be degradable by the occurring in nature microorganism after the use, finally generate carbonic acid gas and water; do not produce toxic gas during burning yet, do not injure human body, free from environmental pollution; this is highly beneficial to protection of the environment, is the environment-friendly material of generally acknowledging.Poly(lactic acid) is added in the polycarbonate resin, significantly improve on the one hand the flowability of material, reduce on the other hand the consumption of petroleum resources.
The exploitation of the thermoplastic material of environment friendly halogen-free fireproof is the direction that the present whole world is paid attention to and developed.Commonly polycarbonate is carried out the halogen-free flameproof modification use organophosphorus, inorganic phosphorus or inorganic hydroxide fire-retardant, fire retardant and matrix phase capacitive are poor, have no the fire-retardant report of introducing halogen-free flame-retardant master batch.
Summary of the invention
The present invention seeks to disclose a kind of halogen-free and flame-retardant polycarbonate mixture and preparation method thereof, the defects that exists to overcome prior art satisfies the needs that association area develops.
Purpose of the present invention can be achieved through the following technical solutions.
A kind of halogen-free and flame-retardant polycarbonate mixture, by weight, its component and content are:
30～50 parts of polycarbonate;
20～45 parts of poly(lactic acid);
15～30 parts of fire-retardant master granules;
Antidrip additive 0.5～1;
Filling modifying agent 2～5;
5～10 parts of compatilizers.
Described polycarbonate resin refers to bisphenol A polycarbonate;
A kind of in poly-L-type lactic acid and the poly-D type lactic acid of described poly(lactic acid).
Described fire-retardant master granule by weight percentage, its component and content are:
Wherein, described bimodal polyethylene for have bimodal in molecular weight distribution and polyethylene more than three peaks (concept of the bimodal polyethylene described in the present invention is with respect to general polyethylene, owing to do not have the poly name of three peak polyethylene or four peaks, have the even polyethylene at five peaks but can prepare in fact again.Therefore, bimodal polyethylene described here is bimodal and the above polyethylene in three peaks).
Described thermo-stabilizer is selected from the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and one or more mixtures in the calixarene, and Main Function is the degraded that produces in the inhibition course of processing.
Described processing aid is selected from one or more mixing in low molecule ester class, metal soap, stearic acid complex ester class and the amides, and Main Function is to improve its processing characteristics.
Described halogen-free flame retardants is selected from P-N type halogen-free environment-friendly type expanding fire retardant, such as HX-IFR102, HX-MMC201, HS-NPS etc.
Described antidrip additive is that styrene-acrylonitrile resin coats tetrafluoroethylene.
Described filling modifying agent is one or more mixtures in calcium carbonate, talcum powder, mica and the polynite.
Described compatilizer is acrylonitrile-butadiene-styrene (ABS) (ABS).
The preparation method of above-mentioned halogen-free and flame-retardant polycarbonate mixture comprises the steps:
1) polycarbonate resin, poly(lactic acid), ABS, fire-retardant master granule, antidrip additive, filling modifying agent are mixed 10-30min in the high speed mixer of 600-1000rpm, fully mix;
2) above-mentioned miscellany being added length-to-diameter ratio is that 36: 1～40: 1, extrusion temperature are that 220-240 ℃, rotating speed are in the strong shearing twin screw extruder of 300-400rpm, melt extrudes, and obtains the finished product after tie rod, cooling, pelletizing, the drying.
Wherein, being prepared as follows of the used fire-retardant master granule of halogen-free and flame-retardant polycarbonate mixture:
Bimodal polyethylene, thermo-stabilizer, processing aid, halogen-free flame retardants are added in proportion, and melting mixing is disperseed in forcing machine, extruding pelletization, final fire-retardant master granule.
The used forcing machine of preparation fire retardant master batch can be that length-to-diameter ratio is 36～40: 1 twin screw extruder, also can be that length-to-diameter ratio is 15～30: 1 single screw extrusion machine.
Product of the present invention had both had excellent flame retardant resistance, had kept simultaneously the good characteristics such as mechanical property.Can satisfy the service requirements of electronics shell, automotive interior structural part based article.Halogen-free and flame-retardant polycarbonate mixture of the present invention adopts the flame-retardant master batch consistency good, adopts twin-screw extrusion equipment, have flow process simple, continuously, the advantage of high, the constant product quality of production efficiency.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with specific embodiment.
Embodiment 1-5
The preparation of halogen-free and flame-retardant polycarbonate mixture of the present invention and physicals see attached list 1, and the testing method standard of employing sees attached list 2.
The polycarbonate resin that adopts in the present embodiment provides for the Dow Chemical Company produces, and the trade mark is 300-10; Poly(lactic acid) 305D; Antidrip additive coats tetrafluoroethylene for the styrene-acrylonitrile resin that Guangzhou entropy energy company limited provides, and the trade mark is SN3307; Filling modifying agent is provided by magnificent source mica factory, and specification is 40 orders; The styrene-acrylonitrile resin trade mark NF2200 that compatilizer is provided by platform company; Bimodal polyethylene PEFB2230 (Borealis); Thermo-stabilizer Irganox 1010 (CIBA company); Halogen-free flame retardants ANTI-610 (oil of SPC research institute).
Embodiment material preparation process is as described below:
1) fire-retardant master granule preparation
Be that melting mixing is disperseed in 15～30: 1 the single screw extrusion machine in length-to-diameter ratio in proportion with bimodal polyethylene, thermo-stabilizer, processing aid, halogen-free flame retardants, extruding pelletization obtains fire-retardant master granule.
2) preparation of anti-flaming polycarbonate ester complexes
With polycarbonate resin, poly(lactic acid), ABS, fire-retardant master granule, antidrip additive, filling modifying agent abundant mixing in high speed mixer; Then miscellany being added length-to-diameter ratio and be 36: 1～40: 1, extrusion temperature and be 200-240 ℃, rotating speed is in the strong shearing twin screw extruder of 300-400rpm, melt extrudes, and obtains the finished product after tie rod, cooling, pelletizing, the drying.
Table 1
| Component (weight) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Polycarbonate | 50 | 45 | 35 | 50 | 30 |
| Poly(lactic acid) | 30 | 30 | 45 | 20 | 45 |
| Fire-retardant master granule | 11.4 | 16.4 | 11.2 | 17.5 | 13.3 |
| Antidrip additive | 0.6 | 0.6 | 0.8 | 0.5 | 0.7 |
| Filling modifying agent | 3 | 3 | 5 | 5 | 5 |
| Compatilizer | 5 | 5 | 7 | 7 | 6 |
| Physicals | |||||
| Melt index | ≥10 | ≥10 | ≥10 | ≥10 | ≥10 |
| Tensile strength | ≥50 | ≥50 | ≥50 | ≥50 | ≥50 |
| Flexural strength | ≥70 | ≥70 | ≥70 | ≥70 | ≥70 |
| Notched Izod impact strength | ≥11 | ≥11 | ≥11 | ≥11 | ≥11 |
| Flame retardant properties | V-0 | V-0 | V-0 | V-0 | V-0 |
Table 2
| Physicals | Testing standard | Unit |
| Melt index | ISO1133：200℃×5kg | g/10min |
| Tensile strength | ISO527/2 | MPa |
| Flexural strength | ISO178 | MPa |
| Notched Izod impact strength | ISO180 | KJ/m 2 |
| Flame retardant properties | UL 94(1.6mm) |
The said products has excellent flame retardant effect, good comprehensive mechanical property and flowability, and its flame retardant properties can reach 1.6mm V-0, melt index 〉=10, tensile strength 〉=50MPa, flexural strength 〉=70MPa, notched Izod impact strength 〉=11KJ/m
2
Environmental protection flame retardant polycarbonate compound of the present invention, can obtain having concurrently the mechanical characteristics of polycarbonate and the useful flowability of poly(lactic acid), matrix material has good flame retardant properties simultaneously, can be advantageously used in the fields such as OA equipment, information, communication equipment, trolley part, material of construction and household electrical appliance.
Above-described embodiment only is preference of the present invention, is not used for limiting the present invention, and all within principle of the present invention, any modifications and variations of doing are all within protection scope of the present invention.
Claims (13)
1. halogen-free and flame-retardant polycarbonate mixture, it is characterized in that: by weight, its component and content are:
30～50 parts of polycarbonate;
20～45 parts of poly(lactic acid);
15～30 parts of fire-retardant master granules;
Antidrip additive 0.5～1;
Filling modifying agent 2～5;
5～10 parts of compatilizers.
2. halogen-free and flame-retardant polycarbonate mixture according to claim 1, it is characterized in that: described polycarbonate resin refers to bisphenol A polycarbonate;
3. halogen-free and flame-retardant polycarbonate mixture according to claim 1 is characterized in that: a kind of in poly-L-type lactic acid and the poly-D type lactic acid of described poly(lactic acid).
4. halogen-free and flame-retardant polycarbonate mixture according to claim 1 is characterized in that: described fire-retardant master granule by weight percentage, its component and content are:
5. halogen-free and flame-retardant polycarbonate mixture according to claim 4, it is characterized in that: described bimodal polyethylene is for to have polyethylene bimodal and more than three peaks in molecular weight distribution.
6. halogen-free and flame-retardant polycarbonate mixture according to claim 4; it is characterized in that: described thermo-stabilizer is selected from the mixture class of phenols, amine, phosphorous acid esters, half Hinered phenols, acryl functional group and monothioester and one or more mixtures in the calixarene, and Main Function is the degraded that produces in the inhibition course of processing.
7. halogen-free and flame-retardant polycarbonate mixture according to claim 4 is characterized in that: described processing aid is selected from one or more mixing in low molecule ester class, metal soap, stearic acid complex ester class and the amides.
8. halogen-free and flame-retardant polycarbonate mixture according to claim 4, it is characterized in that: described halogen-free flame retardants is selected from P-N type halogen-free environment-friendly type expanding fire retardant.
9. halogen-free and flame-retardant polycarbonate mixture according to claim 1 is characterized in that: described antidrip additive is that styrene-acrylonitrile resin coats tetrafluoroethylene.
10. halogen-free and flame-retardant polycarbonate mixture according to claim 1, it is characterized in that: described filling modifying agent is one or more mixtures in calcium carbonate, talcum powder, mica and the polynite.
11. halogen-free and flame-retardant polycarbonate mixture according to claim 1 is characterized in that: described compatilizer is acrylonitrile-butadiene-styrene (ABS).
12. a method for preparing halogen-free and flame-retardant polycarbonate mixture claimed in claim 1 is characterized in that: comprise the steps:
1) polycarbonate resin, poly(lactic acid), ABS, fire-retardant master granule, antidrip additive, filling modifying agent are mixed 10-30min in the high speed mixer of 600-1000rpm, fully mix;
2) above-mentioned miscellany being added length-to-diameter ratio is that 36: 1～40: 1, extrusion temperature are that 220-240 ℃, rotating speed are in the strong shearing twin screw extruder of 300-400rpm, melt extrudes, and obtains the finished product after tie rod, cooling, pelletizing, the drying;
Wherein, being prepared as follows of the used fire-retardant master granule of halogen-free and flame-retardant polycarbonate mixture:
Bimodal polyethylene, thermo-stabilizer, processing aid, halogen-free flame retardants are added in proportion, and melting mixing is disperseed in forcing machine, extruding pelletization, final fire-retardant master granule.
13. preparation method according to claim 12 is characterized in that: the used forcing machine of preparation fire retardant master batch can be that length-to-diameter ratio is 36～40: 1 twin screw extruder, or length-to-diameter ratio is 15～30: 1 single screw extrusion machine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756279A (en) * | 2013-12-31 | 2014-04-30 | 东莞市松燊塑料科技有限公司 | Halogen-free flame retardant PC/PET (polycarbonate/polyethylene terephthalate) alloy and preparation method thereof |
| CN105143348A (en) * | 2013-04-23 | 2015-12-09 | 旭化成化学株式会社 | Thermoplastic resin composition, molded article, and coated molded article |
| CN105647144A (en) * | 2014-11-28 | 2016-06-08 | 黑龙江鑫达企业集团有限公司 | Production method of high-toughness PLA composite material |
| CN111378267A (en) * | 2018-12-28 | 2020-07-07 | 汉达精密电子(昆山)有限公司 | Halogen-free flame-retardant PC/PLA composite material and product thereof |
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| CN101463184A (en) * | 2007-12-21 | 2009-06-24 | 东丽纤维研究所（中国）有限公司 | Flame-retardant polylactic resin and preparation thereof |
| CN101508835A (en) * | 2009-03-12 | 2009-08-19 | 华南理工大学 | Halogen-free flame-proof static resistant polycarbonate composition and method for producing the same |
| CN101787185A (en) * | 2009-02-06 | 2010-07-28 | 深圳市科聚新材料有限公司 | Heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material and preparation method thereof |
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- 2011-08-15 CN CN2011102334569A patent/CN102936403A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101463184A (en) * | 2007-12-21 | 2009-06-24 | 东丽纤维研究所（中国）有限公司 | Flame-retardant polylactic resin and preparation thereof |
| CN101787185A (en) * | 2009-02-06 | 2010-07-28 | 深圳市科聚新材料有限公司 | Heat-resistant halogen-free flame-retardant polylactic acid multi-element composite material and preparation method thereof |
| CN101508835A (en) * | 2009-03-12 | 2009-08-19 | 华南理工大学 | Halogen-free flame-proof static resistant polycarbonate composition and method for producing the same |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105143348A (en) * | 2013-04-23 | 2015-12-09 | 旭化成化学株式会社 | Thermoplastic resin composition, molded article, and coated molded article |
| CN105143348B (en) * | 2013-04-23 | 2016-11-09 | 旭化成株式会社 | Thermoplastic resin composition, molded body and application molded body |
| CN103756279A (en) * | 2013-12-31 | 2014-04-30 | 东莞市松燊塑料科技有限公司 | Halogen-free flame retardant PC/PET (polycarbonate/polyethylene terephthalate) alloy and preparation method thereof |
| CN103756279B (en) * | 2013-12-31 | 2016-04-06 | 东莞市松燊塑料科技有限公司 | A kind of halogen-free flame retardant PC/PET alloy and preparation method thereof |
| CN105647144A (en) * | 2014-11-28 | 2016-06-08 | 黑龙江鑫达企业集团有限公司 | Production method of high-toughness PLA composite material |
| CN111378267A (en) * | 2018-12-28 | 2020-07-07 | 汉达精密电子(昆山)有限公司 | Halogen-free flame-retardant PC/PLA composite material and product thereof |
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