CN101113236A - Non-halogen non-phosphate flame-proof polycarbonate resin and method for preparing same - Google Patents
Non-halogen non-phosphate flame-proof polycarbonate resin and method for preparing same Download PDFInfo
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- CN101113236A CN101113236A CNA2007100453957A CN200710045395A CN101113236A CN 101113236 A CN101113236 A CN 101113236A CN A2007100453957 A CNA2007100453957 A CN A2007100453957A CN 200710045395 A CN200710045395 A CN 200710045395A CN 101113236 A CN101113236 A CN 101113236A
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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
- B29C48/92—Measuring, controlling or regulating
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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
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention relates to a halogen-free, phosphate-free and fire-retardant polycarbonate resin and a preparation method thereof. The invention achieves PC fire resistance effect by adding a set of plasticizer, fire retardant, antiaging dope in PC. Through using the method of the invention, the PC after modified can meet the V-0 grade of UL 94 standard. The halogen-free and phosphate-free fire retardant employed in the invention can reach the comparatively ideal fire-retardant properties by using relatively little fire retardant, which is conformity with the environmental protective requirements of European market; meanwhile, keeps PC of fine mechanical properties and has greater popularization value in the market .
Description
Technical field
The present invention relates to a kind of non-halogen non-phosphate flame-proof polycarbonate resin and preparation method thereof, belong to technical field of polymer materials.
Background technology
Polycarbonate (PC) is a kind of armorphous thermoplastic engineering plastic, formal name used at school 2, and two (4-hydroxy phenyl) the propane polycarbonate of 2-, the most frequently used is bisphenol A polycarbonate.It is called as six big general engineering plastic with ABS, POM, PA, PBT and MODIFIED PP O.Polycarbonate especially is described as plastics it " hat " with the impact strength height owing to have the excellent comprehensive performance.The visible light transmissivity of polycarbonate resin is more than 90%, and has excellent electrical insulating property, extensibility, dimensional stability and chemical resistance, also has from putting out, easily strengthen premium propertiess such as flame retardant resistance, nontoxic, health, easy coloring.Polycarbonate is widely used in every field such as machinery, automobile, space flight and aviation, electronics, electrical equipment, building, information storage, agricultural, communications and transportation.
The application and development of polycarbonate is to develop to compound, the high function of height, customizations, seriation direction, has released the special-purpose separately grade trade mark of multiple products such as CD, automobile, office equipment, casing, packing, medicine, illumination, film at present.Present fire-retardant class polycarbonate is mainly used in field of electronics.The constant electrical insulating property is good insulating material because polycarbonate has good in the temperature of broad, humidity range.Simultaneously, flame retardancy that it is good and dimensional stability make it form wide Application Areas at electronic enterprises.Polycarbonate resin is mainly used in produces various food processing machinery, power tool shell, body, support, freezer compartment of refrigerator drawer and vacuum cleaner part etc.And the important spare part aspect in computer, video cassette recorder and the colour television set of having relatively high expectations for element precision, polycarbonate material has also demonstrated high use value.
The fire retardant that is used for preparing flame-proof polycarbonate resin at present has phosphorus flame retardant, and bromination is gathered carbon, polysiloxane series fire retardant etc.When adding phosphorus flame retardant, make polycarbonate can reach the V-0 rank, will add the fire retardant of more amount, and can cause the resistance toheat of modified polycarbonate sharply to descend, not be suitable in the product as easy heatings such as laptop shells in the heat-resisting equipment that has certain requirements; Polysiloxane series fire retardant mainly has been the synergistic fire retardation, and the flame retardant effect of itself is not quite desirable.
Summary of the invention
The purpose of this invention is to provide a kind of non-halogen non-phosphate flame-proof polycarbonate resin and preparation method thereof with higher heat resisting temperature.
For realizing above purpose, technical scheme of the present invention provides a kind of non-halogen non-phosphate flame-proof polycarbonate resin, it is characterized in that, it is made up of the following weight proportion raw material: PC resinoid 100, silicon-series five-retardant 0.1-5, Sulfonates fire retardant 0.01-2, toughner 0-10, optothermal stabilizer 0.2-2, processing aid 1-5.
Said polycarbonate resin is a kind of or its mixture in the bisphenol A polycarbonate, is PC3030PJ/300-10, PC 300-10/200-10/141R or PC 300-22/EP30.
Said fire retardant is that a kind of or its mixture in siloxanes fire retardant, the sulfonate type fire retardant is B-338 and 1125AC, X-40-9805 and DC-558.
Said optothermal stabilizer is Irganox1010, Irganox168, Irganox1076 or R69.
Said processing aid is silicone oil, white mineral oil, KH-550, KH-560, A-189,101 or the N-ethylene bis stearic acid amide.
A kind of preparation method of non-halogen non-phosphate flame-proof polycarbonate resin is:
A. single stage method:
The first step, take by weighing PC resinoid, silicon-series five-retardant, Sulfonates fire retardant, toughner, optothermal stabilizer, processing aid by weight ratio;
Second the step, with above-mentioned materials thorough mixing in super mixer;
The 3rd goes on foot, with the pay-off of delicate metering the blended starting material is sent in the twin screw extruder then, the high speed shear of screw rod, mixing and carry under, material melted fully, compound, the length-to-diameter ratio of the twin screw extrusion equipment that adopts is at least 32, and have precise dose control and a vacuum-pumping equipment, screw speed is at 100-600 rev/min, it is 230 ℃～260 ℃ in a district that its twin screw is extruded working temperature, 230 ℃～270 ℃ in two districts, 230 ℃～270 ℃ in three districts, 235 ℃～275 ℃ in four districts, residence time 1-2 minute;
The 4th goes on foot, extrudes, tie rod, and cooling, pelletizing obtains finished product at last.
B. or two-step approach:
The first step, take by weighing PC resinoid, silicon-series five-retardant, Sulfonates fire retardant, toughner, optothermal stabilizer, processing aid by weight ratio;
Second step, with PC resin (100 parts), 10%～30% fire retardant and the processing aid of 40%-50% thorough mixing under high-speed stirring, send in the twin screw extruder with the pay-off of delicate metering then, high speed shear at screw rod, mixing following with conveying, material is melted fully, compound, again through extruding, tie rod, cooling, pelletizing obtains a step material, the length-to-diameter ratio of the twin screw extrusion equipment that adopts is at least 32, and have precise dose control and vacuum-pumping equipment, and screw speed is at 100-600 rev/min, and it is 230 ℃～260 ℃ in a district that its twin screw is extruded working temperature, 230 ℃～270 ℃ in two districts, 230 ℃～270 ℃ in three districts, 235 ℃～275 ℃ in four districts, residence time 1-2 minute;
The 3rd goes on foot, a step is expected and remaining fire retardant, toughner, thorough mixing under optothermal stabilizer and the processing aid high-speed stirring is sent in the twin screw extruder by the pay-off of delicate metering, the high speed shear of screw rod, mixing and carry under, material melted fully, compound, again through extruding tie rod, cooling, pelletizing is packaged as finished product at last.The length-to-diameter ratio of the twin screw extrusion equipment that adopts is at least 32, and have precise dose control and a vacuum-pumping equipment, screw speed is at 100-600 rev/min, it is 230 ℃～260 ℃ in a district that its twin screw is extruded working temperature, 230 ℃～270 ℃ in two districts, 230 ℃～270 ℃ in three districts, 235 ℃～275 ℃ in four districts, residence time 1-2 minute;
The fire retardant that the present invention adopts can improve the flame resistivity of material, the adding of toughner can improve the toughness of material, replenish and take out the toughness of material decay that grain causes, photostabilizer can improve aging resistance of materials, and processing aid can effectively improve each component dispersiveness, reduce harmful friction;
Advantage of the present invention is to have higher heat resisting temperature, and flow process is simple, continuous, high, the constant product quality of production efficiency.
Embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment
The PC resinoid is selected the PC3030PJ/300-10 of different viscosity for use, PC 300-10/200-10/141R, PC300-22/EP30, by regulating the flowability that the PC components contents can be regulated material, toughner is selected B-338 and 1125AC for use, can increase the toughness of material, the fire retardant of siloxane series is selected X-40-9805 and DC-558 for use, wherein DC-558 is a liquid, it is the Sulfonates fire retardant that the Sulfonates fire retardant is selected FR-2025 for use, photostabilizer selects 1010 and 168 for use, and processing aid is selected EBS for use, sees attached list 1.
The concrete prescription (part) of subordinate list 1. embodiment correspondences
| Starting material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| PC3030PJ/300-10 | - | 100 | 50 | - | - |
| PC 300-10/200-10/141R PC 300-22/EP30 B-338 1125AC X-40-9805 FR-2025 1010 168 EBS DC-558 | 100 - - - - - - - - - | - - 4 1 0.1 0.1 0.3 0.2 0.3 0.3 | 50 - 4 1 0.2 0.15 0.3 0.2 0.3 0.4 | 50 50 4 1 0.3 0.2 0.3 0.2 0.3 0.5 | - 100 4 1 0.4 0.3 0.3 0.2 0.3 0.5 |
A kind of preparation method of non-halogen non-phosphate flame-proof polycarbonate resin is:
Embodiment 1 and embodiment 2 use single stage method:
The first step, take by weighing PC resinoid, silicon-series five-retardant, Sulfonates fire retardant, toughner, optothermal stabilizer, processing aid by weight ratio;
Second the step, with above-mentioned materials thorough mixing in super mixer;
The 3rd step, with the pay-off of delicate metering the blended starting material are sent in the twin screw extruder then, under the high speed shear of screw rod, mixing and conveying, material melted fully, compound,
The length-to-diameter ratio of the twin screw extrusion equipment that adopts is 40, and have precise dose control and a vacuum-pumping equipment, screw speed is at 100～600 rev/mins, it is 230 ℃～260 ℃ in a district that its twin screw is extruded working temperature, 230 ℃～270 ℃ in two districts, 230 ℃～270 ℃ in three districts, 235 ℃～275 ℃ in four districts, residence time 1-2 minute;
The 4th goes on foot, extrudes, tie rod, and cooling, pelletizing obtains finished product at last.
Embodiment 3 and embodiment 4 use two-step approach:
The first step, take by weighing PC resinoid, silicon-series five-retardant, Sulfonates fire retardant, toughner, optothermal stabilizer, processing aid by weight ratio;
Second step, with the PC resin, 10%～30% fire retardant and the processing aid of 40%-50% thorough mixing under high-speed stirring, send in the twin screw extruder with the pay-off of delicate metering then, high speed shear at screw rod, mixing following with conveying, material is melted fully, compound, again through extruding, tie rod, cooling, pelletizing obtains a step material, the length-to-diameter ratio of the twin screw extrusion equipment that adopts is 40, and have precise dose control and vacuum-pumping equipment, and screw speed is at 100～600 rev/mins, and it is 230 ℃～260 ℃ in a district that its twin screw is extruded working temperature, 230 ℃～270 ℃ in two districts, 230 ℃～270 ℃ in three districts, 235 ℃～275 ℃ in four districts, residence time 1-2 minute;
The 3rd the step, with the PC resin, one step material and remaining fire retardant, toughner, thorough mixing under optothermal stabilizer and the processing aid high-speed stirring, send in the twin screw extruder by the pay-off of delicate metering, the high speed shear of screw rod, mixing and carry under, material melted fully, compound, again through extruding, tie rod, cooling, pelletizing is packaged as finished product at last.The length-to-diameter ratio of the twin screw extrusion equipment that adopts is 40, and have precise dose control and a vacuum-pumping equipment, screw speed is at 100～600 rev/mins, it is 230 ℃～260 ℃ in a district that its twin screw is extruded working temperature, 230 ℃～270 ℃ in two districts, 230 ℃～270 ℃ in three districts, 235 ℃～275 ℃ in four districts, residence time 1-2 minute;
The mixture of each embodiment preparation is injection molded into the standard batten of testing usefulness by standard size, and the physicals among each embodiment is respectively by China's national standard and U.S. UL standard testing, and is as shown in the table.
| Physicals | Testing method |
| The molten incendivity that refers to of tensile strength elongation at break Izod notched Izod impact strength flexural strength modulus in flexure | ASTM D638 ASTM D638 ASTM D256 ASTM D790 ASTM D790 ASTM D1238 UL94 |
The properties of sample of subordinate list 2. embodiment correspondences
| Starting material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Tensile strength MPa | 60.6 | 61.2 | 60.7 | 61.4 | 60.8. |
| Elongation % | ＞100 | ＞100 | ＞100 | ＞100 | ＞100 |
| Notch shock J/m | 798 | 835 | 803 | 741 | 653 |
| Flexural strength MPa | 85.4 | 83.5 | 83 | 84.8 | 82.6 |
| Modulus in flexure MPa | 2207 | 2151 | 2153 | 2292 | 2187 |
| The molten g/10min that refers to | 10.9 | 5.4 | 8.6 | 14.2 | 23.1 |
| Flame retardant rating | 3.0mmV-2 | 2.0mmV-0 | 2.0mmV-0 | 3.0mmV-0 | 1.5mmV-0 |
As seen, adopt the flame-retardant system of non-halogen non-phosphate among the present invention, can use less fire retardant consumption to reach more satisfactory flame retardant properties, the PC that obtains can reach UL94 standard V-0 rank, meet the environmental protection i requirement in American-European market, simultaneously can keep the PC excellent mechanical property, on market, have bigger promotional value.
Claims (6)
1. a non-halogen non-phosphate flame-proof polycarbonate resin is characterized in that, it is made up of the following weight proportion raw material: PC resinoid 100, silicon-series five-retardant 0.1-5, Sulfonates fire retardant 0.01-2, toughner 0-10, optothermal stabilizer 0.2-2, processing aid 1-5.
2., a kind of non-halogen non-phosphate flame-proof polycarbonate resin according to claim 1 is characterized in that, said polycarbonate resin is a kind of or its mixture in the bisphenol A polycarbonate, be PC3030PJ/300-10, PC 300-10/200-10/141R or PC 300-22/EP30.
3. a kind of non-halogen non-phosphate flame-proof polycarbonate resin according to claim 1, it is characterized in that, said fire retardant is a kind of or its mixture in siloxanes fire retardant, the sulfonate type fire retardant, is B-338 and 1125AC, X-40-9805 and DC-558.
4. a kind of non-halogen non-phosphate flame-proof polycarbonate resin according to claim 1 is characterized in that, said optothermal stabilizer is Irganox1010, Irganox168, Irganox1076 or R69.
5. a kind of non-halogen non-phosphate flame-proof polycarbonate resin according to claim 1 is characterized in that, said processing aid is silicone oil, white mineral oil, KH-550, KH-560, A-189,101 or the N-ethylene bis stearic acid amide.
6. the preparation method of a kind of non-halogen non-phosphate flame-proof polycarbonate resin according to claim 1 is:
A. single stage method:
The first step, take by weighing PC resinoid, silicon-series five-retardant, Sulfonates fire retardant, toughner, optothermal stabilizer, processing aid by weight ratio;
Second the step, with above-mentioned materials thorough mixing in super mixer;
The 3rd goes on foot, with the pay-off of delicate metering the blended starting material is sent in the twin screw extruder then, the high speed shear of screw rod, mixing and carry under, material melted fully, compound, the length-to-diameter ratio of the twin screw extrusion equipment that adopts is at least 32, and have precise dose control and a vacuum-pumping equipment, screw speed is at 100～600 rev/mins, it is 230 ℃ 2～260 ℃ in a district that its twin screw is extruded working temperature, 230 ℃～270 ℃ in two districts, 230 ℃ 2～270 ℃ in three districts, 235 ℃～275 ℃ in four districts, residence time 1-2 minute;
The 4th goes on foot, extrudes, tie rod, and cooling, pelletizing obtains finished product at last.
B. or two-step approach:
The first step, take by weighing PC resinoid, silicon-series five-retardant, Sulfonates fire retardant, toughner, optothermal stabilizer, processing aid by weight ratio;
Second step, with the PC resin, 10%～30% fire retardant and the processing aid of 40%-50% thorough mixing under high-speed stirring, send in the twin screw extruder with the pay-off of delicate metering then, high speed shear at screw rod, mixing following with conveying, material is melted fully, compound, again through extruding, tie rod, cooling, pelletizing obtains a step material, the length-to-diameter ratio of the twin screw extrusion equipment that adopts is at least 32, and have precise dose control and vacuum-pumping equipment, and screw speed is at 100～600 rev/mins, and it is 230 ℃～260 ℃ in a district that its twin screw is extruded working temperature, 230 ℃～270 ℃ in two districts, 230 ℃～270 ℃ in three districts, 235 ℃～275 ℃ in four districts, residence time 1-2 minute;
The 3rd step, with the PC resin, one step material and remaining fire retardant, toughner, thorough mixing under optothermal stabilizer and the processing aid high-speed stirring, send in the twin screw extruder by the pay-off of delicate metering, high speed shear at screw rod, mixing following with conveying, material is melted fully, compound, again through extruding, tie rod, cooling, pelletizing is packaged as finished product at last, the length-to-diameter ratio of the twin screw extrusion equipment that adopts is at least 32, and have precise dose control and vacuum-pumping equipment, and screw speed is at 100～600 rev/mins, and it is 230 ℃～260 ℃ in a district that its twin screw is extruded working temperature, 230 ℃～270 ℃ in two districts, 230 ℃～270 ℃ in three districts, 235 ℃～275 ℃ in four districts, residence time 1-2 minute;
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007100453957A CN101113236A (en) | 2007-08-30 | 2007-08-30 | Non-halogen non-phosphate flame-proof polycarbonate resin and method for preparing same |
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| CNA2007100453957A CN101113236A (en) | 2007-08-30 | 2007-08-30 | Non-halogen non-phosphate flame-proof polycarbonate resin and method for preparing same |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920534A (en) * | 2009-06-16 | 2010-12-22 | 飞雕电器集团有限公司 | Waste material recovery method |
| CN102040820A (en) * | 2010-12-30 | 2011-05-04 | 深圳市科聚新材料有限公司 | Television casing material and preparation method thereof |
| CN102558808A (en) * | 2010-12-28 | 2012-07-11 | 合肥杰事杰新材料股份有限公司 | Environment-friendly flame-retardant scratch-resistant polycarbonate resin and preparation method thereof |
| CN102936391A (en) * | 2011-08-15 | 2013-02-20 | 上海金发科技发展有限公司 | Halogen and phosphorus-free flame-retardant antistatic ABS resin and its preparation method |
| CN103044867A (en) * | 2012-12-25 | 2013-04-17 | 江苏金发科技新材料有限公司 | Composite and reinforced PBT material and preparation method thereof |
| CN103160101A (en) * | 2011-12-13 | 2013-06-19 | 合肥杰事杰新材料股份有限公司 | Halogen-free flame retardant PC material with high fluidity, and preparation method thereof |
| CN103275475A (en) * | 2013-04-25 | 2013-09-04 | 深圳市兴盛迪新材料有限公司 | Polycarbonate composition and preparation method thereof |
| CN103524688A (en) * | 2013-10-25 | 2014-01-22 | 安徽省富光实业股份有限公司 | Polycarbonate composite material with stable quality for cup shell and preparation method thereof |
| CN106419820A (en) * | 2016-09-26 | 2017-02-22 | 江阴市人民医院 | Surgical instrument for thoracoscope |
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| CN110615987A (en) * | 2019-10-15 | 2019-12-27 | 山东省科学院能源研究所 | Halogen-free flame-retardant toughened nylon and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101920534A (en) * | 2009-06-16 | 2010-12-22 | 飞雕电器集团有限公司 | Waste material recovery method |
| CN102558808A (en) * | 2010-12-28 | 2012-07-11 | 合肥杰事杰新材料股份有限公司 | Environment-friendly flame-retardant scratch-resistant polycarbonate resin and preparation method thereof |
| CN102040820A (en) * | 2010-12-30 | 2011-05-04 | 深圳市科聚新材料有限公司 | Television casing material and preparation method thereof |
| CN102040820B (en) * | 2010-12-30 | 2012-11-28 | 深圳市科聚新材料有限公司 | Television casing material and preparation method thereof |
| CN102936391B (en) * | 2011-08-15 | 2016-10-12 | 上海金发科技发展有限公司 | A kind of halogen-free phosphorus-free inflaming retarding antistatic ABS resinoid and preparation method thereof |
| CN102936391A (en) * | 2011-08-15 | 2013-02-20 | 上海金发科技发展有限公司 | Halogen and phosphorus-free flame-retardant antistatic ABS resin and its preparation method |
| CN103160101A (en) * | 2011-12-13 | 2013-06-19 | 合肥杰事杰新材料股份有限公司 | Halogen-free flame retardant PC material with high fluidity, and preparation method thereof |
| CN103044867A (en) * | 2012-12-25 | 2013-04-17 | 江苏金发科技新材料有限公司 | Composite and reinforced PBT material and preparation method thereof |
| CN103044867B (en) * | 2012-12-25 | 2016-01-20 | 江苏金发科技新材料有限公司 | Composite strengthening PBT material and preparation method thereof |
| CN103275475A (en) * | 2013-04-25 | 2013-09-04 | 深圳市兴盛迪新材料有限公司 | Polycarbonate composition and preparation method thereof |
| CN103275475B (en) * | 2013-04-25 | 2015-05-06 | 深圳市兴盛迪新材料有限公司 | Polycarbonate composition and preparation method thereof |
| CN103524688A (en) * | 2013-10-25 | 2014-01-22 | 安徽省富光实业股份有限公司 | Polycarbonate composite material with stable quality for cup shell and preparation method thereof |
| CN106419820A (en) * | 2016-09-26 | 2017-02-22 | 江阴市人民医院 | Surgical instrument for thoracoscope |
| CN106751593A (en) * | 2017-01-18 | 2017-05-31 | 东莞市票友机电科技有限公司 | Binder motor mount PBT engineering plastics and motor mount |
| CN106751593B (en) * | 2017-01-18 | 2019-06-21 | 东莞市票友机电科技有限公司 | Binder motor mount PBT engineering plastics and motor mount |
| CN110615987A (en) * | 2019-10-15 | 2019-12-27 | 山东省科学院能源研究所 | Halogen-free flame-retardant toughened nylon and preparation method and application thereof |
| CN110615987B (en) * | 2019-10-15 | 2022-08-16 | 山东省科学院能源研究所 | Halogen-free flame-retardant toughened nylon and preparation method and application thereof |
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