CN101362857B - Non-halogen flame-retarding high performance polycarbonate engineering plastics and preparation method thereof - Google Patents
Non-halogen flame-retarding high performance polycarbonate engineering plastics and preparation method thereof Download PDFInfo
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- CN101362857B CN101362857B CN2008101987176A CN200810198717A CN101362857B CN 101362857 B CN101362857 B CN 101362857B CN 2008101987176 A CN2008101987176 A CN 2008101987176A CN 200810198717 A CN200810198717 A CN 200810198717A CN 101362857 B CN101362857 B CN 101362857B
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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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
Abstract
The invention relates to a halogen-free inflaming retarding high-performance polycarbonate engineering plastic and a preparation method thereof. Counted in weight percentage, the components of the engineering plastic include as follows: 78 to 92 percent of PC resin, 5 to 10 percent of sulfur-bearing super engineering plastics, 0.1 to 3 percent of flame retardant containing silicon, 0.1 to 1 percent of anti-dropping agent, 1 to 5 percent of compatilizers and 0.1 to 1 percent of chemical inhibitors; wherein, the sulfur-bearing engineering resin is polyethersulfone or the composition of the polyethersulfone and polyphenyl thioether; the flame retardant containing silicon is acrylic ester graft modification polysiloxane or the composition of the acrylic ester graft modification polysiloxane and poly methyl phenyl siloxane. The preparation method includes as follows: the materials of the prescription are fully mixed in a high speed mixer; then is fed into a co-rotating meshed double-screw extruder to melt, blend and extrude. In the invention, the sulfur-bearing super engineering plastics and the flame retardant containing silicon are matched and used, thus endowing the polycarbonate with excellent flame retardation and higher heat resistance as well as excellent compatibility, improving the mechanical property of the composite material and overcoming the defects of being easily separated out and absorbing moisture of a micromolecule flame retardant containing silicon.
Description
Technical field
The present invention relates to a kind of non-halogen flame-retarding high performance polycarbonate (PC) engineering plastics and preparation method thereof, can be applicable to deck, charger, junctor, liquid crystal panel, thermal printer, higher temperature line ring framework and plasm TV heat radiation window etc. to the heat-resisting and fire-retardant key components and parts that has high requirements, belong to the new chemical materials technical field.
Background technology
The basic composite engineering plastics of polycarbonate (PC) is the thermoplastic resin based composite material of a class excellent property, have high impulse strength, thermotolerance and dimensional stability, be widely used as making the starting material of all types of industries spare and accessory parts, as various shells of electronics and driving member, office equipment and other industrial application.These are used and to require all generally that material is fire-retardant to have higher heat-drawn wire simultaneously, therefore the basic composite engineering plastics of polycarbonate (PC) are carried out fire-retardantly and heat resistance modified just seeming very necessary.
The basic composite engineering plastics of present fire-retardant class polycarbonate (PC) has generally used the phosphoric acid ester fire retardant of more small molecular weight or with Poly Brominated Diphenyl Ethers and the polybrominated biphenyl material halogen-containing flame retardant as representative.The former molecular weight is less to be in a liquid state at normal temperatures; resistance toheat to the basic composite engineering plastics of polycarbonate (PC) has big negative impact; reduced the heat-resistant deforming temperature; and the latter since in recent years countries in the world the pay attention to day by day of environment protection and health of human body is all clearly provided against use in files such as the RoHS of European Union instruction.And the present progress of making rapid progress along with development of science and technology especially power electronics industry, various electronic devices and components are towards Highgrade integration and microminiaturized development, operating frequency constantly is the lifting of the order of magnitude simultaneously, cause the device heating amount sharply to rise, this just has higher requirement to the flame-retardance and thermal endurance of the widely used plastic items material of these industries.
Realize that from fire retardant and fire retarding synergist that polymerization stage sets about changing the molecular structure of polycarbonate (PC) or adding specific type the fire-retardant and heat-resisting purpose of taking into account is feasible and obvious results in theory.But the former is owing to relate to the improvement upgrading of production of resins equipment and synthetic route etc., invest huge, production cycle is very long, practice is got up difficult, having limited it applies, and the synthetic difficulty of the fire retardant of specific type and fire retarding synergist, price is high, and in application, there is inconvenience, easily separate out the moisture absorption and the good toughness of PC material is had certain destruction such as the Sulfonates fire retardant that uses at present, and it can not satisfy the fire-retardant requirement of some particular product such as thin wall parts when using separately.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of and have that comprehensive mechanical property is good, good heat resistance, flame retardant effect obviously, the fire retardant addition is little, performance steady and the non-halogen flame-retarding high performance polycarbonate engineering plastics of handling ease and preparation method thereof.
For realizing above purpose, the present invention is used sulfur-bearing engineering plastics and siliceous fire retardant, give polycarbonate modified engineering plastics good flame retardancy and higher heat-drawn wire, design can improve the mechanical property and the processing characteristics of matrix material based on consistency good between each component, overcomes small molecules sulfur-bearing fire retardant and easily separates out shortcomings such as the moisture absorption.Concrete technical scheme is as follows:
A kind of halogen-free and flame-retardant polycarbonate engineering plastics is characterized in that, are made up of following materials in percentage by mass:
PC resin 86～92%;
The special engineered resin 5～10% of sulfur-bearing;
Siliceous fire retardant 0.1～3%;
Antidrip agent 0.1～1%;
Compatilizer 1～5%;
Oxidation inhibitor 0.1～1%;
Described PC resin is the bisphenol A-type aromatic copolycarbonate, the L-1225Y or the L-1250Y of preferred Japanese TEIJIN company, the 121R of GE company or 141R; The special engineered resin of described sulfur-bearing be Poly-s 179 (PES) or with the title complex of polyphenylene sulfide (PPS), PES and PPS mass ratio are 4～1: 1, wherein Poly-s 179 is E2010, the E3010 of BASF AG, a kind of or its mixture of E1010, polyphenylene sulfide is Fortron 0205 or the 0220A9 of Polyplastics, both all preferred good powdery resins of dispersing property; Described siliceous fire retardant be esters of acrylic acid graft modification polysiloxane (ACR-g-Si) or with the compound of PSI (PMPSi), ACR-g-Si and PMPSi mass ratio are 4～2: 1.Wherein ACR-g-Si is the organic polysilsesquioxane graft copolymer of acrylate/high phenyl, polyacrylic ester and the mol ratio of high phenyl sesquisiloxane in graft copolymer are 0.4～1.3: 1, can select the relevant silicon-series five-retardant of DowCorning company for use or according to application number 200510033478.5 or 200610123965.5 disclosed methods preparations; Antidrip agent is granular polytetrafluoroethylene PTFE with fibrosis ability, or mass ratio is the tetrafluoroethylene of 3～1:1 and the compound of polyvinylidene difluoride (PVDF), fluorine-containing Antidrip agent FA-500, TS-AD001, the D-20CE of the preferred DAIKIN of Antidrip agent company; Described compatilizer is a kind of of styrene-maleic anhydride copolymer (SMA), MBS (MBS) or their title complex, and SMA and MBS mass ratio are 7～1:1; Described oxidation inhibitor is binary antioxidant system or ternary antioxidant system, for hindered phenol anti-oxidants Irganox1010, Irganox1076 and phosphite ester kind antioxidant Irganox168 press the composite use of mass ratio 4～2:1, also can add content again and be 15～25% benzofuranones of above-mentioned binary antioxidant system total amount and form the efficient antioxidant system of ternary, B225, B900, the IrganoxGX2225 of the preferred Ciba Special of oxidation inhibitor Chemical company.
The making method of a kind of non-halogen flame-retarding high performance polycarbonate (PC) engineering plastics is:
The first step, it is standby that PC resin and other raw materials are carried out thorough drying;
Second step, the special engineered resin of accurate measurement PC resin and sulfur-bearing by mass percentage, siliceous fire retardant, Antidrip agent, compatilizer, oxidation inhibitor;
The 3rd step is with above-mentioned materials thorough mixing in super mixer;
The 4th step, to mix sufficient starting material by automatic feeding sends in the same way in the meshed double screw forcing machine, the high speed shear of the heat transfer of barrel and screw rod, mixing and carry under, material carries out sufficient fusion, dispersion and compound, the length-to-diameter ratio of the twin screw extrusion equipment that adopts is at least 32, screw speed is at 100～500 rev/mins, it is 230 ℃～260 ℃ of feeding sections that its twin screw is extruded working temperature, 245 ℃～280 ℃ of fusion plastification sections, mix 235 ℃～270 ℃ of homogenizing zones, 230 ℃～250 ℃ of melt Conveying metering zones, 1～2 minute residence time;
In the 5th step, melt extrude, tie rod, water cooling, granulation sieve drying, obtain finished product at last.
With respect to prior art, the present invention has following advantage and beneficial effect:
The present invention utilizes composite modification technology on the basis that has kept the original good mechanical property of PC resin, resistance toheat and processing characteristics, thereby utilized Poly-s 179, polyphenylene sulfide molecular structure in combustion heat decomposition course, can be decomposed to form the acid source material PC has been played the condensed phase fire retardation, both use separately or also with the use that can greatly reduce even replace fully expensive small molecules Sulfonates fire retardant, add polyphenylene sulfide and also have the effect of regulating processing fluidity.Because sulfur-bearing special engineering plastics such as Poly-s 179 and polyphenylene sulfide and PC resin compatible are good, do not add or add the minute quantity compatilizer and just can obtain to be better than raw-material mechanical property, obtain higher heat-resistant deforming temperature.Siliceous based flame retardant not only can cooperate and plays the cooperative flame retardant effect with the above-mentioned special engineered resin of element sulphur that contains, and has the effect of certain interface modifier, also helps improving composite materials property.Therefore the non-halogen flame-retarding high performance polycarbonate engineering plastics of the present invention's preparation can satisfy the multiple requirement of certain applications to polycarbonate-base composite engineering plastics high-strength temperature-resistant halogen-free flameproof.
Embodiment
The invention will be further described below in conjunction with embodiment, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1～6
The PC resin is selected the L-1250Y of Japanese TEIJIN company for use.
The PES resin is selected the E2010 of BASF for use.
The PPS resin is selected the 0220A9 of Polyplastics for use.
Siliceous fire retardant (FRSi) adopts esters of acrylic acid graft modification siloxanes (ACR-g-Si), and its preparation can be synthesized according to application number 200710032309.9 disclosed methods, PSI (PMPSi).
Antidrip agent is selected the fluorine-containing Antidrip agent TS-AD001 of DAIKIN company, homemade PVDF for use.
Compatilizer is selected homemade SMA, MBS for use.
Oxidation inhibitor is selected binary oxidation inhibitor B225, B900 or the ternary oxidation inhibitor GX2225 of Ciba Special Chemical company for use.
Embodiment and contain sulfonate fire retardant KSS (for Sloss industrial product) reference prescription such as table 1 shows.
During preparation, PC resin that drying is good and the special engineered resin of sulfur-bearing, siliceous fire retardant, Antidrip agent, compatilizer, oxidation inhibitor thorough mixing 2～3 minutes in super mixer is standby, to mix raw material metering completely by automatic metering system, and material is sent in the same way in the meshed double screw forcing machine, in the heat transfer of barrel and the high speed shear of screw rod by automatic feeder, mixing following with conveying, material carries out sufficient fusion, dispersion and compound, the length-to-diameter ratio of the twin screw extrusion equipment that adopts is 40, dispose accurate temperature controlling instruments and vacuum-pumping equipment, screw speed is at 300 rev/mins, and it is 230 ℃～260 ℃ of feeding sections that its twin screw is extruded working temperature, 245 ℃～280 ℃ of fusion plastification sections, mix 235 ℃～270 ℃ of homogenizing zones, 230 ℃～250 ℃ of melt Conveying metering zones, 1～2 minute residence time; Extrude, tie rod, water cooling, granulation sieve drying, obtain non-halogen flame-retarding high performance polycarbonate engineering plastics at last.
The composite engineering plastics that above embodiment is made carries out molding preparation test with the standard batten and carry out following various performance test by relevant criterion: mechanical property and heat-resistant deforming performance are according to the GB standard, and flame retardant properties is according to the UL94V standard, and is as shown in table 2.
Table 1 Example formulations and reference prescription
Table 2 composite material test method
Embodiment typical case performance data is summarized in the table 3:
The embodiment test result as can be seen from table 3, the UL-94 vertical combustion experiment of embodiment all can be by the test of V-0@1.6mm level, LOI has more obviously raising, the heat-resistant deforming temperature makes moderate progress, do not affect the mechanical properties simultaneously, the high tenacity that has particularly kept the PC material preferably, the shock strength of some prescription even increase wherein, net effect is better than Sulfonates fire retardant.
The performance of table 3 embodiment correspondence
Claims (7)
1. halogen-free and flame-retardant polycarbonate engineering plastics is characterized in that, by percentage to the quality, its composition of raw materials consists of:
PC resin 86～92%;
Sulfur-bearing engineering resin 5～10%;
Siliceous fire retardant 0.1～3%;
Antidrip agent 0.1～1%;
Compatilizer 1～5%;
Oxidation inhibitor 0.1～1%;
Described sulfur-bearing engineering resin is a Poly-s 179, or the title complex of Poly-s 179 and polyphenylene sulfide, and Poly-s 179 and polyphenylene sulfide mass ratio are 4～1: 1;
Described siliceous fire retardant is an esters of acrylic acid graft modification polysiloxane, or the compound of esters of acrylic acid graft modification polysiloxane and PSI, its mass ratio is 4～2: 1, wherein esters of acrylic acid graft modification polysiloxane is the organic polysilsesquioxane graft copolymer of acrylate and high phenyl, and polyacrylic ester and the mol ratio of high phenyl sesquisiloxane in graft copolymer are 0.4～1.3: 1.
2. a kind of halogen-free and flame-retardant polycarbonate engineering plastics according to claim 1 is characterized in that described PC resin is the bisphenol A-type aromatic copolycarbonate.
3. a kind of halogen-free and flame-retardant polycarbonate engineering plastics according to claim 1 is characterized in that described Antidrip agent is a tetrafluoroethylene, or mass ratio is 3～1: 1 the tetrafluoroethylene and the compound of polyvinylidene difluoride (PVDF).
4. a kind of halogen-free and flame-retardant polycarbonate engineering plastics according to claim 1, it is characterized in that, described compatilizer is a kind of of styrene-maleic anhydride copolymer, MBS or their mixture, and its mass ratio is 7～1: 1.
5. a kind of halogen-free and flame-retardant polycarbonate engineering plastics according to claim 1, it is characterized in that, described oxidation inhibitor is binary oxidation inhibitor, and described binary oxidation inhibitor is hindered phenol anti-oxidants Irganox1010 or Irganox1076 and phosphite ester kind antioxidant Irganox168 by mass ratio 4～2: 1 is composite.
6. a kind of halogen-free and flame-retardant polycarbonate engineering plastics according to claim 1, it is characterized in that, described oxidation inhibitor is ternary oxidation inhibitor, and described ternary oxidation inhibitor is that the benzofuranones that adds 15～25% mass parts on binary oxidation inhibitor basis is formed.
7. the making method of a kind of halogen-free and flame-retardant polycarbonate engineering plastics according to claim 1 is:
The first step, PC resin, sulfur-bearing engineering resin, siliceous fire retardant, Antidrip agent, compatilizer and oxidation inhibitor thorough drying are standby in will filling a prescription;
In second step, by mass percentage, take by weighing PC resin, sulfur-bearing engineering resin, siliceous fire retardant, Antidrip agent, compatilizer and oxidation inhibitor, thorough mixing in super mixer;
The 3rd step, to mix sufficient starting material sends in the same way in the meshed double screw forcing machine, the high speed shear of the heat transfer of barrel and screw rod, mixing and carry under, material carries out sufficient fusion, dispersion and compound, the length-to-diameter ratio of the twin screw extrusion equipment that adopts is at least 32, screw speed is at 100～500 rev/mins, it is 230 ℃～260 ℃ of feeding sections that its twin screw is extruded working temperature, 245 ℃～280 ℃ of fusion plastification sections, mix 235 ℃～270 ℃ of homogenizing zones, 230 ℃～250 ℃ of melt Conveying metering zones, 1～2 minute residence time;
In the 4th step, melt extrude, tie rod, water cooling, granulation sieve drying, obtain finished product at last.
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| CN106189232A (en) * | 2016-08-23 | 2016-12-07 | 怀远县金浩电子科技有限公司 | A kind of preparation method of the special plastic cement of temperature relay shell |
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| CN101792585B (en) * | 2010-03-16 | 2011-12-14 | 广州市番禺区天宇塑料实业有限公司 | Flame-retardant polycarbonate composition and preparation method thereof |
| CN101812225B (en) * | 2010-04-01 | 2011-12-07 | 华南理工大学 | Flame retardant polycarbonate material with high surface hardness and gloss and preparation method thereof |
| CN102382439B (en) * | 2010-12-14 | 2012-10-17 | 重庆文理学院 | Modified polycarbonate and preparation method thereof |
| CN102329489A (en) * | 2011-05-31 | 2012-01-25 | 深圳市科聚新材料有限公司 | Needle flame grade semitransparent PC (polycarbonate) material for anti-collision strip and preparation method thereof |
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| CN114644820A (en) * | 2020-12-18 | 2022-06-21 | 湖南登科材料科技有限公司 | High-temperature-resistant halogen-free flame-retardant special engineering plastic and preparation method thereof |
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Application publication date: 20090211 Assignee: Dongguan Yuankai Plastic Co., Ltd. Assignor: South China University of Technology Contract record no.: 2015440000134 Denomination of invention: Non-halogen flame-retarding high performance polycarbonate engineering plastics and preparation method thereof Granted publication date: 20110504 License type: Exclusive License Record date: 20150514 |
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