CN112538248A - Flame-retardant polycarbonate composite material and preparation method and application thereof - Google Patents
Flame-retardant polycarbonate composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN112538248A CN112538248A CN202011371255.0A CN202011371255A CN112538248A CN 112538248 A CN112538248 A CN 112538248A CN 202011371255 A CN202011371255 A CN 202011371255A CN 112538248 A CN112538248 A CN 112538248A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- polycarbonate
- siloxane
- block copolymer
- mbs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a flame-retardant polycarbonate composite material which mainly comprises polycarbonate resin, siloxane-polycarbonate block copolymer, sulfonate flame retardant, phosphorus-containing flame retardant and MBS. The addition of the flame retardant can obtain good flame retardance, and the siloxane-aromatic polycarbonate block copolymer with a special structure and MBS are further added, so that the defect of overhigh internal stress after various components are mixed can be overcome, and the ultrasonic welding performance is improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant polycarbonate composite material and a preparation method and application thereof.
Background
Ultrasonic welding is to transmit ultrasonic energy through materials, vibrate to generate heat to reach the melting point of a welding point, and after a certain pressure is applied, the surface of the welding rod is fused through intermolecular entanglement. At present, the ultrasonic welding does not need welding flux, is convenient and quick, has short time, and is widely applied to the aspects of plastic film packaging, tail lamp welding, large-scale part connection and the like. Ultrasonic welding is a convenient welding mode, and is widely applied to connection of automobile tail lamps at the present stage.
However, due to the large molecular volume of the polycarbonate, the entanglement mobility of molecular chains on the surface of the welding rod after the melting of the ultrasonic welding is weak, and the molecular chains are not stretched enough, so that the local internal stress of a product is high, and the part with the high local internal stress is easy to crack when the external force impacts, such as a ball drop test. Particularly, the addition of the toughening agent can further reduce the activity capability of molecular chains so as to increase internal stress, so that the local internal stress of the ultrasonic-welded workpiece is increased, and the capability of the workpiece for resisting external impact force is reduced.
Disclosure of Invention
The invention aims to provide a polycarbonate composite material which has the advantages of good flame retardant effect and good ultrasonic welding.
The invention also aims to provide a preparation method and application of the flame-retardant polycarbonate composite material.
The invention is realized by the following technical scheme:
the flame-retardant polycarbonate composite material comprises the following components in parts by weight:
100 parts of polycarbonate resin;
5-30 parts of siloxane-polycarbonate block copolymer;
0.01-1 part of sulfonate flame retardant
0.01-10 parts of phosphorus-containing flame retardant;
MBS 1-10 parts;
the weight ratio of siloxane-polycarbonate block copolymer to MBS was in the range of (6-1): 1;
in the siloxane-polycarbonate block copolymer, the weight content of silicon is 3-9wt%, and the weight average molecular weight is 17000-25000;
the rubber content range of the MBS is 5-80%.
Preferably, the weight ratio of siloxane-polycarbonate block copolymer to MBS is in the range of (3-1): 1.
preferably, the siloxane-polycarbonate block copolymer has a weight average molecular weight in the range of 19000-22000.
The sulfonate flame retardant is at least one selected from tetraethylammonium perfluoroethane sulfonate, potassium diphenylsulfone sulfonate, potassium perfluoroalkyl sulfonate, potassium benzenesulfonyl and sodium p-toluenesulfonate.
The phosphorus-containing flame retardant is selected from at least one of hexaphenoxycyclotriphosphazene, triphenyl phosphate, resorcinol-bis (diphenyl phosphate), bisphenol A-bis (diphenyl phosphate) and resorcinol bis [ bis (2, 6-dimethylphenyl phosphate) ].
Preferably, the weight average molecular weight of the polycarbonate is 19000-25000.
Preferably, the rubber content range of the MBS is 50-75%, and the rubber particle diameter range is 200-500 nm.
The full name of MBS is a methyl methacrylate-butadiene-styrene terpolymer. In MBS, the rubber content refers to the content of the rubber component containing double bonds in the toughening agent. The rubber content and the rubber particle diameter range of MBS also influence the flame retardance.
The preparation method of the flame-retardant polycarbonate composite material comprises the following steps: the polycarbonate resin, the siloxane-polycarbonate block copolymer, the sulfonate flame retardant, the phosphorus-containing flame retardant and the MBS are uniformly mixed and extruded and granulated by a double-screw extruder, wherein the temperature range of the screw is 230-260 ℃, and the rotating speed range is 30-80 rpm.
The application of the flame-retardant polycarbonate composite material is suitable for preparing ultrasonic welding parts.
The invention has the following beneficial effects
The sulfonate flame retardant in the flame retardant system of the PC has the advantages of small addition amount and good flame retardant effect. However, the addition of flame retardants such as sulfonate can cause the reduction of ultrasonic weldability, and the defect can be relieved by compounding the phosphorus-containing flame retardant. Furthermore, by adding the siloxane-polycarbonate block copolymer with a special structure (silicon content and weight average molecular weight) and the MBS (rubber content and rubber particle diameter) with a special structure, the defect of overhigh internal stress after mixing of various components can be overcome, and the ultrasonic welding performance is improved.
Detailed Description
The present invention is described in more detail by the following examples, but the present invention is not limited by the following examples.
The raw materials used in the present invention are derived from commercially available products:
polycarbonate A: the weight average molecular weight is 19000, which is corresponding to Mitsubishi PC H-2000F;
polycarbonate B: the weight average molecular weight is 24000, corresponding to Mitsubishi PC S-2000F;
polycarbonate C: the weight average molecular weight is 33000, corresponding to Mitsubishi PC E-1000F;
polycarbonate D: the weight average molecular weight is 15000, and the light emitting PC POLYCARBONATE RESIN TARFLON FN1500 is used;
siloxane-polycarbonate block copolymer a: the weight average molecular weight is 19000, and the weight content of silicon is 5 wt%;
siloxane-polycarbonate block copolymer B: the weight average molecular weight is 22000, and the weight content of silicon is 9 wt%;
siloxane-polycarbonate block copolymer C: the weight average molecular weight was 17500, and the weight content of silicon was 3 wt%;
siloxane-polycarbonate block copolymer D: the weight average molecular weight was 25000, and the weight content of silicon was 5 wt%;
siloxane-polycarbonate block copolymer E: the weight average molecular weight was 25000, and the weight content of silicon was 20 wt%;
siloxane-polycarbonate block copolymer F: the weight average molecular weight is 35000, and the weight content of silicon is 7 wt%;
siloxane-polycarbonate block copolymer G: the weight average molecular weight was 13000, and the weight content of silicon was 4 wt%;
MBS-A: the rubber content is 60 percent, and the rubber particle size range is 400 nm;
MBS-B: the rubber content is 75%, and the rubber particle size range is 200 nm;
MBS-C: the rubber content is 23 percent, and the rubber particle size range is 700 nm;
MBS-D: the rubber content is 80 percent, and the rubber particle size range is 100 nm;
ABS: the rubber content is 85 percent, and the rubber particle size range is 80 nm;
silicon-containing rubber: the rubber content is 32 percent, and the rubber particle size range is 200 nm;
sodium p-toluenesulfonate: is sold on the market;
triphenyl phosphate: is sold on the market;
bisphenol a-bis (diphenyl phosphate): is sold on the market;
the performance test method comprises the following steps:
(1) baking a sample at 120 ℃ for 4-6 hours, forming an upper cover part and a lower cover part with ultrasonic rays at 280 ℃ on an injection molding machine, welding the upper cover part and the lower cover part into a box part by using ultrasonic welding equipment by adopting a process of welding current 0.5A and welding time 0.2S, standing for 24 hours, smashing 500g of steel balls with the diameter of 1.3m to fall on a welding line position, and grading the states of the tested parts, wherein the grades correspond to the following steps:
| state of the article | Without cracking | Slight cracking, crack less than 2cm | Slight cracking, crack greater than 2cm | The upper and lower shells are directly cracked | Severe cracking, falling of broken pieces of the shell |
| Grade of welding | Level 0 | Level 1 | Stage 2 | Grade 3 | 4 stage |
(2) Baking the sample at 120 ℃ for 4-6 hours, then performing injection molding on the sample on an injection molding machine at 280 ℃ to obtain a UL 94 standard combustion sample strip with the thickness of 1.5mm, adjusting the humidity of 55% at 23 ℃ for 48 hours after molding, performing combustion test according to the UL 94 standard, and judging the flame retardant grade.
Table 1: EXAMPLES 1-4 flame retardant polycarbonate composites content of Components (parts by weight) and test results
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Polycarbonate A | 100 | |||
| Polycarbonate B | 100 | |||
| Polycarbonate C | 100 | |||
| Polycarbonate D | 100 | |||
| Siloxane-polycarbonate Block copolymer A | 8 | 8 | 8 | 8 |
| MBS-A | 5 | 5 | 5 | 5 |
| Sodium p-toluenesulfonate | 0.1 | 0.1 | 0.1 | 0.1 |
| Phosphoric acid triphenyl ester | 3 | 3 | 3 | 3 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-0 |
| Grade of welding | 0 | 1 | 2 | 2 |
As is clear from examples 1 to 4, the weight average molecular weight of the polycarbonate is preferably within the range of 19000-25000.
Table 2: examples 5 to 7 and comparative examples 1 to 3 flame retardant polycarbonate composites content of each component (parts by weight) and test results
| Example 5 | Example 6 | Example 7 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Polycarbonate A | 100 | 100 | 100 | 100 | 100 | 100 |
| Siloxane-polycarbonate Block copolymer B | 8 | |||||
| Siloxane-polycarbonate block copolymer C | 8 | |||||
| Siloxane-polycarbonate block copolymer D | 8 | |||||
| Siloxane-polycarbonate block copolymer E | 8 | |||||
| Siloxane-polycarbonate block copolymer F | 8 | |||||
| Siloxane-polycarbonate block copolymer G | 8 | |||||
| MBS-A | 5 | 5 | 5 | 5 | 5 | 5 |
| Sodium p-toluenesulfonate | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Phosphoric acid triphenyl ester | 3 | 3 | 3 | 3 | 3 | 3 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 |
| Grade of welding | 0 | 1 | 1 | 3 | 4 | 3 |
From example 1/5/6/7, it is preferable that the siloxane-polycarbonate block copolymer has a weight average molecular weight of 19000-22000. Further, according to comparative examples 1 to 3, it is understood that the weight average molecular weight and the silicon content of the siloxane-polycarbonate block copolymer are critical parameters, and the technical effects of the present invention cannot be achieved when these parameters are out of the ranges defined by the present invention.
Table 3: examples 8 to 10 and comparative examples 4 to 5 flame retardant polycarbonate composites content of each component (parts by weight) and test results
| Example 8 | Example 9 | Example 10 | Comparative example 4 | Comparative example 5 | |
| Polycarbonate A | 100 | 100 | 100 | 100 | 100 |
| Siloxane-polycarbonate Block copolymer A | 8 | 8 | 8 | 8 | 8 |
| MBS-B | 5 | ||||
| MBS-C | 5 | ||||
| MBS-D | 5 | ||||
| ABS | 5 | ||||
| Silicon-containing rubber | 5 | ||||
| Sodium p-toluenesulfonate | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Phosphoric acid triphenyl ester | 3 | 3 | 3 | 3 | 3 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-1 | V-0 |
| Grade of welding | 1 | 2 | 2 | 2 | 3 |
As can be seen from example 1/8/9/10, the preferred range of MBS is 50-75%, and the range of particle size is 200-500 nm.
It can be seen by comparison example 4/5 that ABS and silicone-containing rubber tougheners commonly used in the polycarbonate art can reduce the ultrasonic weldability of PC.
Table 4: examples 11 to 16 and comparative examples 6 to 7 flame-retardant polycarbonate composite materials were prepared in respective component amounts (parts by weight) and test results
| Example 11 | Example 12 | Example 13 | Example 14 | Example 15 | Example 16 | Comparative example 6 | Comparative example 7 | |
| Polycarbonate A | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Siloxane-polycarbonate Block copolymer A | 17 | 16.5 | 16 | 15 | 13.3 | 10 | 6.67 | 17.8 |
| MBS-A | 3 | 3.5 | 4 | 5 | 6.7 | 10 | 13.3 | 2.2 |
| Sodium p-toluenesulfonate | 0.5 | 0.1 | 0.5 | 0.5 | 0.5 | 0.5 | 0.1 | 0.1 |
| Phosphoric acid triphenyl ester | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 | V-0 |
| Grade of welding | 2 | 1 | 1 | 0 | 0 | 0 | 3 | 3 |
As can be seen from Table 4, the parts by weight of the siloxane-polycarbonate block copolymer and MBS need to be in the range of (6-1): 1, preferably (3-1): 1.
table 5: EXAMPLES 17-19 flame-retardant polycarbonate composite materials the contents of the respective components (parts by weight) and
| example 17 | Example 18 | Example 19 | |
| Polycarbonate A | 100 | 100 | 100 |
| Siloxane-polycarbonate Block copolymer A | 5 | 30 | 8 |
| MBS-A | 1 | 10 | 5 |
| Sodium p-toluenesulfonate | 0.1 | 0.1 | 0.1 |
| Phosphoric acid triphenyl ester | 3 | 3 | |
| Bisphenol A-bis (diphenyl phosphate) | 8 | ||
| Flame retardant rating | V-1 | V-0 | V-0 |
| Grade of welding | 2 | 0 | 0 |
Table 6: comparative examples 8 to 11 flame-retardant polycarbonate composite materials in respective component contents (parts by weight) and Properties
| Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 | |
| Polycarbonate A | 100 | 100 | 100 | 100 |
| Siloxane-polycarbonate Block copolymer A | 8 | 8 | 8 | 50 |
| MBS-A | 5 | 5 | 10 | |
| Sodium p-toluenesulfonate | 0.1 | 0.5 | 0.1 | 0.1 |
| Bisphenol A-bis (diphenyl phosphate) | 3 | 3 | ||
| Flame retardant rating | V-1 | V-0 | V-0 | V-0 |
| Grade of welding | 2 | 3 | 3 | 4 |
It can be seen from comparative example 8/9/10 that the sulfonate flame retardant has excellent flame retardant effect, but the ultrasonic weldability of the polycarbonate composite material is lowered.
As can be seen from comparative example 10, the siloxane-polycarbonate block copolymer needs to be compounded with MBS to achieve improved ultrasonic welding performance.
From comparative example 11, it is understood that, although the flame retardancy is better as the amount of the siloxane-polycarbonate block copolymer added is larger, the ultrasonic weldability starts to deteriorate when it exceeds 30 parts.
Claims (9)
1. The flame-retardant polycarbonate composite material is characterized by comprising the following components in parts by weight:
100 parts of polycarbonate resin;
5-30 parts of siloxane-polycarbonate block copolymer;
0.01-1 part of sulfonate flame retardant
0.01-10 parts of phosphorus-containing flame retardant;
MBS 1-10 parts;
the weight ratio of siloxane-polycarbonate block copolymer to MBS was in the range of (6-1): 1;
in the siloxane-polycarbonate block copolymer, the weight content of silicon is 3-9wt%, and the weight average molecular weight is 17000-25000;
the rubber content range of the MBS is 5-80%.
2. The flame retardant polycarbonate composite of claim 1, wherein the weight ratio of siloxane-polycarbonate block copolymer to MBS is in the range of (3-1): 1.
3. the flame retardant polycarbonate composite of claim 1, wherein the siloxane-polycarbonate block copolymer has a weight average molecular weight in the range of 19000-22000.
4. The flame retardant polycarbonate composite of claim 1, wherein the sulfonate salt flame retardant is selected from at least one of tetraethylammonium perfluoroethane sulfonate, potassium diphenylsulfone sulfonate, potassium perfluoroalkylsulfonate, potassium phenylsulfonylbenzenesulfonate, sodium p-toluenesulfonate.
5. The flame retardant polycarbonate composite of claim 1, wherein the phosphorus-containing flame retardant is selected from at least one of hexaphenoxycyclotriphosphazene, triphenyl phosphate, resorcinol-bis (diphenyl phosphate), bisphenol a-bis (diphenyl phosphate), resorcinol bis [ bis (2, 6-dimethylphenyl phosphate) ].
6. The flame retardant polycarbonate composite of claim 1, wherein the polycarbonate has a weight average molecular weight of 19000-25000.
7. The flame retardant polycarbonate composite of claim 1, wherein the rubber content of MBS is in the range of 50-75% and the rubber average particle diameter is in the range of 200-500 nm.
8. The method of preparing a flame retardant polycarbonate composite of any of claims 1-7, comprising the steps of: uniformly mixing bisphenol A type polycarbonate resin, siloxane-polycarbonate block copolymer, sulfonate flame retardant, phosphorus-containing flame retardant and MBS, and extruding and granulating by a double-screw extruder, wherein the temperature range of the screw is 230-260 ℃, and the rotating speed range is 30-80 rpm.
9. Use of the flame retardant polycarbonate composite of any one of claims 1-7, for the preparation of an ultrasonically welded article.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011371255.0A CN112538248B (en) | 2020-11-30 | 2020-11-30 | Flame-retardant polycarbonate composite material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011371255.0A CN112538248B (en) | 2020-11-30 | 2020-11-30 | Flame-retardant polycarbonate composite material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112538248A true CN112538248A (en) | 2021-03-23 |
| CN112538248B CN112538248B (en) | 2022-05-17 |
Family
ID=75016431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011371255.0A Active CN112538248B (en) | 2020-11-30 | 2020-11-30 | Flame-retardant polycarbonate composite material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112538248B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1890320A (en) * | 2003-10-16 | 2007-01-03 | 通用电气公司 | Light-colored polycarbonate compositions and preparation methods |
| CN101056942A (en) * | 2004-10-04 | 2007-10-17 | 通用电气公司 | Flame retardant thermoplastic polycarbonate compositions, use thereof and method of its manufacture |
| US20080176990A1 (en) * | 2004-08-16 | 2008-07-24 | General Electric Company | Polycarbonate compositions, articles, and method of manufacture |
| US8399546B2 (en) * | 2004-08-05 | 2013-03-19 | Sabic Innovative Plastics Ip B.V. | Flame retardant thermoplastic compositions having EMI shielding |
| CN103408913A (en) * | 2013-08-16 | 2013-11-27 | 惠州市沃特新材料有限公司 | Composite flame-retardant polycarbonate material, and preparation method and application thereof |
-
2020
- 2020-11-30 CN CN202011371255.0A patent/CN112538248B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1890320A (en) * | 2003-10-16 | 2007-01-03 | 通用电气公司 | Light-colored polycarbonate compositions and preparation methods |
| US8399546B2 (en) * | 2004-08-05 | 2013-03-19 | Sabic Innovative Plastics Ip B.V. | Flame retardant thermoplastic compositions having EMI shielding |
| US20080176990A1 (en) * | 2004-08-16 | 2008-07-24 | General Electric Company | Polycarbonate compositions, articles, and method of manufacture |
| CN101056942A (en) * | 2004-10-04 | 2007-10-17 | 通用电气公司 | Flame retardant thermoplastic polycarbonate compositions, use thereof and method of its manufacture |
| CN103408913A (en) * | 2013-08-16 | 2013-11-27 | 惠州市沃特新材料有限公司 | Composite flame-retardant polycarbonate material, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHIH, WC: "Synthesis and characterization of polycarbonate/polydimethylsiloxane multiblock copolymer prepared from dimethylsiloxane and various aromatic dihydroxyl monomers", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| 王璐: "超声波焊接条件对PC/ABS与PMMA焊接强度的影响", 《工程塑料应用》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112538248B (en) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106589618A (en) | Halogen-free flame retardant dynamically vulcanized EPDM/PP thermoplastic elastomer and preparation method thereof | |
| CN105419106B (en) | A kind of halogen-free flame-retardant resin and preparation method thereof | |
| CN112250935A (en) | High-flame-retardant-grade low-smoke halogen-free material and preparation method and application thereof | |
| CN109651749A (en) | Resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant and its preparation method and application | |
| CN109627568A (en) | Polyolefine cable sheath material and preparation method thereof | |
| CN103030877B (en) | Impact-resistant polypropylene composite and preparation method thereof | |
| CN108102222B (en) | Stress whitening resistant master batch, stress whitening resistant halogen-free expansion flame-retardant polypropylene composite material and preparation method thereof | |
| WO2022095361A1 (en) | Flame retardant polyamide composite material, preparation method therefor, and application thereof | |
| CN113462067A (en) | Halogen-free flame-retardant EVA cable material composite material and preparation method thereof | |
| CN109280259B (en) | EVA/PA6 flame-retardant composite material added with OMMT in distribution regulation and control mode and preparation method | |
| CN109535681B (en) | Alloy material for high-fluidity thin-wall product and preparation method thereof | |
| CN113462108B (en) | Degradable organic-inorganic flame-retardant composite material based on core-shell structure | |
| CN112538248B (en) | Flame-retardant polycarbonate composite material and preparation method and application thereof | |
| CN112852133B (en) | Anti-droplet PLA/PVA composite material and preparation method thereof | |
| CN104693599A (en) | Method for preparing halogen-free flame retardant polypropylene modified material | |
| CN109777070B (en) | Ultralow-gloss PC/ABS resin composition and preparation method thereof | |
| CN104341755A (en) | PC (Polycarbonate) antistatic masterbatch | |
| CN114196200A (en) | Preparation method of flame retardant-free low-flammability polyamide material | |
| CN110054890B (en) | Bio-based PA56 composite material with high flame retardance and preparation method thereof | |
| CN112679826A (en) | Flame-retardant polyethylene composition and preparation method thereof | |
| JP3788493B2 (en) | Norbornene resin composition | |
| CN116041933B (en) | Halogen-free high-temperature-resistant flame-retardant ABS composite PC alloy material and preparation method and application thereof | |
| CN109337186B (en) | Doped nano SiO2Composite EVA/PA6 alloy flame-retardant material and preparation method thereof | |
| CN112961428B (en) | Halogen-free flame-retardant polypropylene composite suitable for new energy automobile and application and preparation method thereof | |
| CN115322709B (en) | Hot melt adhesive film with high metal adhesion and good flame retardance and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |