CN112745651B - Flame-retardant polycarbonate composition and preparation method and application thereof - Google Patents
Flame-retardant polycarbonate composition and preparation method and application thereof Download PDFInfo
- Publication number
- CN112745651B CN112745651B CN202011482729.9A CN202011482729A CN112745651B CN 112745651 B CN112745651 B CN 112745651B CN 202011482729 A CN202011482729 A CN 202011482729A CN 112745651 B CN112745651 B CN 112745651B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- polycarbonate composition
- retardant polycarbonate
- flame
- calcium sulfate
- 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.)
- Active
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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- 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
Abstract
The invention relates to a flame-retardant polycarbonate composition, a preparation method and application thereof. The flame-retardant polycarbonate composition comprises polycarbonate, calcium fluoride, calcium sulfate, a complexing agent, a flame retardant, an anti-dripping agent and other processing aids. The flame-retardant polycarbonate composition provided by the invention has the advantages of high infrared transmittance, low visible light transmittance, good toughness, proper fluidity and good appearance quality.
Description
Technical Field
The invention belongs to the field of engineering plastics, and particularly relates to a flame-retardant polycarbonate composition, and a preparation method and application thereof.
Background
The existing commonly used infrared-transmitting plastic is a material with an infrared-transmitting function obtained by adding different organic toner into transparent resin after blending, but the technical means can only realize a black infrared-transmitting effect, and is only applied to the field of remote controller shell materials at present. Aiming at the requirement of the communication industry on 5G signal transmission, the development trend of intelligent home is remote control intelligent development, so that different household appliance shells have satisfied infrared ray penetration capacity, and the practicability is greatly limited if the shell material is only a black transparent material. At present, some white materials which can transmit infrared rays are reported, for example, patent CN101723420A discloses magnesium fluoride powder, and an infrared optical element obtained by hot-pressing the magnesium fluoride powder has high transmittance in an infrared band. However, magnesium fluoride is generally added to carbonates as a filler, and when it is added, the color of the polycarbonate system can be reduced, but when it is added in a large amount, the desired infrared transmittance can be obtained. However, the addition of a large amount of filler greatly influences the toughness of the polycarbonate and the visible light transmittance; in addition, degraded gas marks and water marks are generated during processing, which affect the appearance quality of the product.
Therefore, it is important to develop a polycarbonate material having excellent toughness to ensure safety and excellent appearance quality while satisfying the requirements for infrared transmission and visible light transmission.
Disclosure of Invention
The invention aims to overcome the defect or defect that the shell material is only black in the prior art, and provides a flame-retardant polycarbonate composition. The flame-retardant polycarbonate composition provided by the invention has the advantages of higher infrared transmittance, lower visible light transmittance, better toughness and better appearance quality.
Another object of the present invention is to provide a method for preparing the above flame retardant polycarbonate composition.
The invention also aims to provide application of the flame-retardant polycarbonate composition in preparing communication or intelligent household shell materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a flame-retardant polycarbonate composition comprises the following components in parts by weight:
at present, the development of flame retardants is mature, and the polycarbonate system can be endowed with better flame retardant performance by adding conventional flame retardants in the field, so that a flame-retardant polycarbonate system is obtained; there are still major technical obstacles to flame retardant polycarbonate systems that technically balance the lower visible light transmission requirements and have satisfactory infrared transmission.
Researches find that white calcium fluoride and calcium sulfate both have a certain infrared transmission effect, and the addition of the calcium fluoride and the calcium sulfate is expected to lighten the color of a polycarbonate system and improve the infrared transmission rate. However, the infrared transmittance meeting the requirements can be achieved only by adding a large amount of calcium fluoride, the improvement of the infrared transmittance is limited even if a large amount of calcium sulfate is added, the toughness and the flowability of a polycarbonate system are remarkably reduced due to the large amount of added calcium fluoride or calcium sulfate, and active metals in the calcium fluoride and calcium sulfate have potential degradation hazards on a PC resin matrix, and also generate degradation gas marks and water marks during processing, so that the appearance quality of a product is influenced.
Through multiple researches, the inventor of the invention finds that when calcium fluoride and calcium sulfate are simultaneously added into polycarbonate, the high infrared transmittance and the low visible light transmittance can be achieved under the condition of a small addition amount through the blending of the use amounts of the calcium fluoride and the calcium sulfate, the better toughness is ensured (under the condition of not adding a toughening agent), and the negative hidden trouble influence on the fluidity and the appearance quality is reduced to a certain extent. Wherein, the proper amount of the calcium fluoride plays a main role in improving the infrared transmittance, and the proper amount of the calcium sulfate plays a main role in reducing the visible light transmittance. Meanwhile, the addition of a small amount of complexing agent can stabilize the degradation hidden danger of the active metal to the PC resin matrix, and ensure the fluidity and the appearance grade stability of the finished piece in the process of processing and forming.
Through the synergistic effect of calcium fluoride, calcium sulfate and a complexing agent, the flame-retardant polycarbonate composition provided by the invention has the advantages of higher infrared transmittance, lower visible light transmittance, better toughness, proper fluidity and better appearance quality.
Preferably, the flame retardant polycarbonate composition comprises the following components in parts by weight:
preferably, the polycarbonate has a weight average molecular weight of greater than 40000.
Preferably, the content of impurity zinc in the calcium fluoride is not higher than 500ppm (for example, 100-500 ppm).
The inevitable presence of impurities in calcium fluoride, such as zinc, in amounts such as to be too great, will affect the infrared transmission (the infrared transmission will be reduced) and also result in poor thermal stability of the material.
Preferably, the oil absorption value of the calcium sulfate is 20-30, and further preferably 22-26.
The oil absorption value of the calcium sulfate is measured by the following method: gradually adding a reagent dioctyl phthalate into a certain calcium sulfate sample, fully stirring the mixture into a conglobation, and leaching without excessive reagent to increase the mass of the reagent to calculate the oil absorption value of the calcium sulfate sample.
The lower the oil absorption value of the calcium sulfate, the powder is easy to agglomerate, and the too high oil absorption value easily causes processing defects. The certain oil absorption value can increase the dispersibility of the filler in matrix resin within a limited range, so that the infrared transmittance is further improved, and the toughness and the rigidity of the material are better balanced.
Preferably, the complexing agent is one or more of citric acid and salts thereof (such as potassium citrate, sodium citrate and the like), aminocarboxylic acids (such as ethylenediamine tetraacetic acid, aminotriacetic acid and the like), hydroxylamine-based carboxylic acids (such as dihydroxyethyl glycine) or organic polyphosphonic acids (such as diphosphonic acid, triphosphonic acid and the like).
Flame retardants, anti-drip agents conventional in the art may be used in the present invention.
Preferably, the flame retardant is one or more of a brominated flame retardant, a phosphorus-nitrogen flame retardant, a sulfur flame retardant or a silicon flame retardant.
Preferably, the anti-dripping agent is polytetrafluoroethylene.
Polytetrafluoroethylene (PTFE) is commercially available, for example as an aqueous solution comprising PTFE, and coated PTFE, such as Metablen A-3800, CCAS9002-94-0, containing approximately 50% by weight of a methyl acrylate/butyl acrylate copolymer.
Other processing aids conventional in the art may also be used in the present invention.
Preferably, the other processing aids are one or more of antioxidants, heat stabilizers or lubricants.
Antioxidants include organophosphites such as tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite; alkylated monophenols or polyphenols; the alkylation reaction product of a polyphenol with a diene (e.g., tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxyhydrocinnamate) ] methane); butylated reaction products of p-cresol or dicyclopentadiene; alkylated hydroquinones; hydroxylated thiodiphenyl ethers; alkylidene-bisphenols; a benzyl compound; esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with mono-or polyhydric alcohols; esters of beta- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with mono-or polyhydric alcohols; esters of thioalkyl or thioaryl compounds, such as distearylthiopropionate, dilaurylthiopropionate, ditridecylthiodipropionate, octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol-tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; esteramines of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, or a combination comprising at least two of the foregoing antioxidants.
The weight portion of the antioxidant is 0.01-0.1.
Heat stabilizers include organophosphites such as triphenyl phosphite, tris (2, 6-dimethylphenyl) phosphite and tris- (mixed mono-and di-nonylphenyl) phosphite; phosphonates (such as dimethylbenzene phosphonate, phosphates such as trimethyl phosphate); or combinations comprising at least two of the foregoing heat stabilizers.
The heat stabilizer is 0.01-0.1 part by weight.
Lubricants include metal stearates, stearyl stearate, pentaerythritol tetrastearate, beeswax, montan wax, paraffin wax, and the like; or a combination comprising at least two of the foregoing lubricants.
The heat stabilizer is 0.1-1 part by weight.
Preferably, the flame retardant polycarbonate composition has an ASTM notched impact of greater than 400J/m; when the thickness is 2mm, the infrared transmittance is not lower than 60%, and the visible light transmittance is not higher than 45%.
The preparation method of the flame-retardant polycarbonate composition comprises the following steps: mixing polycarbonate, calcium fluoride, calcium sulfate, a complexing agent, a flame retardant, an anti-dripping agent and other processing aids to obtain a premix, and then extruding and granulating to obtain the flame-retardant polycarbonate composition.
Preferably, the stirring time is 1-3 min.
Preferably, the stirring is performed in a high-speed mixer.
The application of the flame-retardant polycarbonate composition in preparing communication or intelligent household shell materials is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
through the synergistic effect of calcium fluoride, calcium sulfate and a complexing agent, the flame-retardant polycarbonate composition provided by the invention has the advantages of higher infrared transmittance, lower visible light transmittance, better toughness, proper fluidity and better appearance quality.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Some of the reagents selected in the examples and comparative examples of the present invention are described below:
polycarbonate 1#, S-2000F, Mitsubishi, Japan, weight average molecular weight is 46000;
polycarbonate 2#, H-3000F, Mitsubishi, Japan, weight average molecular weight 23000;
calcium fluoride No. 1, calcium fluoride, Shanghai Mecline, and the content of impurity zinc is not more than 350 ppm;
calcium fluoride No. 2, calcium fluoride, alatin and impurity zinc content of 520-670 ppm;
calcium sulfate # 1, barium sulfate, Xinjia chemical, oil absorption value is 26;
calcium sulfate 2#, barium sulfate, alatin, oil absorption value is 32;
complexing agent No. 1, EDTA, and sea chemical engineering;
complexing agent # 2, MD1024, BASF;
flame retardants, BDP, adico;
anti-drip agent, POLYTS 30X, Korean Pacific, 50% AS coating;
antioxidant 1076, BASF;
thermal stabilizers, 168, BASF;
lubricant, PETS, Longsha Chemicals.
The test methods for the properties of the flame retardant polycarbonate compositions of the examples of the present invention and the comparative examples are as follows:
MI: on a melt index instrument with the set temperature of 300 ℃, according to the ISO1133 standard, the test condition of 1.2kg load is selected, the set weight of the particles to be tested is weighed, the melt index is tested within the retention time of 240s, and the data is recorded to calculate the melt index MI of the material. The degradation stability of the material can be judged by the size of the MI, if the MI is more than 80, the material is degraded, if the MI is more than 100, the material cannot be tested, and the material is unstable and is recorded as being not tested.
Impact strength: 3.0mm IZOD notched impact strength was measured according to ASTM D256; the notch type is an injection molded notch, wherein the higher the impact strength, the better the material toughness.
Infrared transmittance: and (3) placing the plate with the thickness of 2.0mm and the diameter of not less than 50mm under a specified injection molding process under a 940nm infrared transmittance tester for testing, and recording infrared transmittance data.
Visible light transmittance: and (3) placing the plate with the thickness of 2.0mm and the diameter of not less than 50mm under the specified injection molding process under a 380-780nm transmittance tester for testing, and recording the visible light transmittance data.
Degradation of gas marks and water bloom: the injection temperature was set at 300 ℃ and the water splash mold (mold temperature 100 ℃) was evaluated at a prescribed injection pressure and injection speed, and the air marks and water splash were observed from the injection near end to the injection far end, and the evaluation was judged to be excellent if no surface defects were observed, while the evaluation was judged to be poor if less than 5 defects were observed at the injection near end but no defects were observed at the injection far end, and the evaluation was judged to be poor if defects were observed at both the injection near end and the injection far end.
The preparation process of the flame retardant polycarbonate compositions of the examples and comparative examples of the present invention is as follows: weighing polycarbonate, calcium fluoride, calcium sulfate, a complexing agent, a flame retardant, an anti-dripping agent and other processing aids (if any) according to the proportion, stirring and blending for 1-3 min in a high-speed mixer to obtain a premix, then extruding, and performing a granulation process to obtain the flame-retardant polycarbonate composition.
Examples 1 to 13
This example provides a series of flame retardant polycarbonate compositions having the components set forth in Table 1.
TABLE 1 Components (parts) of flame retardant polycarbonate compositions provided in examples 1 to 13
Examples 14 to 18
This example provides a series of flame retardant polycarbonate compositions having the components set forth in Table 2.
TABLE 2 Components (parts) of flame retardant polycarbonate compositions provided in examples 14 to 18
Comparative examples 1 to 6
This comparative example provides a series of flame retardant polycarbonate compositions having the components as shown in Table 3.
TABLE 3 Components (parts) of flame retardant polycarbonate compositions provided in comparative examples 1 to 6
The properties of the flame retardant polycarbonate compositions of the respective examples and comparative examples were measured according to the above-mentioned test methods, and the results are shown in Table 4.
TABLE 4 Performance test results of the flame retardant polycarbonate compositions of the examples and comparative examples
As can be seen from Table 4, the flame retardant polycarbonate compositions provided in the examples of the present invention have high IR transmittance, low visible light transmittance, good toughness and fluidity, and good appearance quality. Wherein, in a certain range, the infrared light transmittance is increased along with the increase of the addition amount of the calcium fluoride, the visible light transmittance is reduced, the fluidity is slightly poor, and the toughness is slightly improved and then slightly deteriorated; however, if only calcium fluoride (comparative example 5) is added to increase the transmittance of infrared light, a large amount of calcium fluoride is added, but the toughness of the polycarbonate resin is seriously affected, and the PC resin matrix is degraded, the fluidity is significantly increased, and the appearance quality is poor. Within a certain range, the infrared light transmittance is increased along with the increase of the addition amount of calcium sulfate, the visible light transmittance is reduced, the flowability is slightly poor, and the toughness is slightly improved and then slightly deteriorated; however, when calcium sulfate is added alone (as in comparative example 6), even if it is added in a large amount, the improvement of the infrared transmittance is limited, the visible light transmittance is significantly reduced, but the toughness of the polycarbonate resin is affected, and the PC resin matrix is degraded, the fluidity is significantly increased, and the appearance quality is poor. In contrast, in comparative example 1, calcium fluoride and calcium sulfate are not added, so that the infrared ray transmission effect is avoided, the visible light transmittance is high, and the toughness is poor under the condition that no flexibilizer is added; meanwhile, no complexing agent is added in the comparative example 1, so that the influence on the flowability is small; comparative example 2 no complexing agent was added, and the PC resin was degraded due to the active metals in calcium fluoride and calcium sulfate, and the fluidity was significantly increased and could not be tested; comparative example 3 has no calcium fluoride, has good fluidity, but cannot ensure the infrared transmittance, has limited reduction of the visible light transmittance, and has poor toughness of the resin system because no flexibilizer is added; comparative example 4 does not add calcium sulfate, the fluidity is better, but the visible light transmittance is too large, the infrared light transmittance is improved to a limited extent, and the toughness of the resin system is not good without adding a toughening agent.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art, having the benefit of this disclosure, may effect numerous modifications thereto and changes may be made without departing from the scope of the invention in its aspects.
Claims (10)
1. The flame-retardant polycarbonate composition is characterized by comprising the following components in parts by weight:
the complexing agent is one or more of citric acid and salts thereof, amino carboxylic acids, hydroxyl amino carboxylic acids or organic polyphosphonic acid.
2. The flame retardant polycarbonate composition of claim 1, comprising the following components in parts by weight:
3. the flame retardant polycarbonate composition of claim 1, wherein the polycarbonate has a weight average molecular weight of greater than 40000.
4. The flame retardant polycarbonate composition of claim 1, wherein the calcium fluoride has a zinc impurity content of not greater than 500 ppm.
5. The flame retardant polycarbonate composition of claim 1, wherein the calcium sulfate has an oil absorption value of 20 to 30.
6. The flame retardant polycarbonate composition of claim 1, wherein the flame retardant is one or more of a brominated flame retardant, a phosphorus-nitrogen flame retardant, a sulfur flame retardant or a silicon flame retardant; the anti-dripping agent is polytetrafluoroethylene.
7. The flame retardant polycarbonate composition of claim 1, wherein the other processing aid is one or more of an antioxidant, a heat stabilizer, or a lubricant.
8. The flame retardant polycarbonate composition of claim 1, wherein the flame retardant polycarbonate composition has an ASTM notched impact of not less than 400J/m; when the thickness is 2mm, the infrared transmittance is not lower than 60%, and the visible light transmittance is not higher than 45%.
9. The method for preparing the flame retardant polycarbonate composition of any one of claims 1 to 8, comprising the steps of: and stirring and mixing the polycarbonate, the calcium fluoride, the calcium sulfate, the complexing agent, the flame retardant, the anti-dripping agent and other processing aids to obtain a premix, and then extruding and granulating to obtain the flame-retardant polycarbonate composition.
10. The use of the flame retardant polycarbonate composition of any one of claims 1 to 8 in the preparation of a housing material for communications or smart homes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011482729.9A CN112745651B (en) | 2020-12-15 | 2020-12-15 | Flame-retardant polycarbonate composition and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011482729.9A CN112745651B (en) | 2020-12-15 | 2020-12-15 | Flame-retardant polycarbonate composition and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112745651A CN112745651A (en) | 2021-05-04 |
| CN112745651B true CN112745651B (en) | 2022-05-20 |
Family
ID=75648491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011482729.9A Active CN112745651B (en) | 2020-12-15 | 2020-12-15 | Flame-retardant polycarbonate composition and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112745651B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113637309B (en) * | 2021-08-17 | 2022-08-19 | 金发科技股份有限公司 | Flame-retardant polycarbonate alloy composition with high thermal stability and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5481773B2 (en) * | 2007-08-08 | 2014-04-23 | 三菱エンジニアリングプラスチックス株式会社 | Aromatic polycarbonate resin composition and molded article thereof |
| CN103374214A (en) * | 2012-04-25 | 2013-10-30 | 黑龙江鑫达企业集团有限公司 | High-impact environment-friendly flame-retardant PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy material and preparation technology thereof |
| CN103992607B (en) * | 2013-09-16 | 2016-10-05 | 宁波力达得为高分子科技有限公司 | A kind of saturating ultrared polymethylmethacrylacomposition composition |
| CN104017344B (en) * | 2013-09-16 | 2017-01-11 | 宁波力达得为高分子科技有限公司 | Infrared-transparent polycarbonate composition |
| WO2017216680A1 (en) * | 2016-06-15 | 2017-12-21 | Sabic Global Technologies B.V. | Multilayer structures and methods of forming the same |
-
2020
- 2020-12-15 CN CN202011482729.9A patent/CN112745651B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112745651A (en) | 2021-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112724630B (en) | Infrared-transmitting flame-retardant polycarbonate composition and preparation method and application thereof | |
| CN107501887B (en) | High-performance polycarbonate composition containing SAG compatilizer with special structure and preparation method thereof | |
| CN110760175A (en) | Toughened PC/SI-PC/PBT alloy material and preparation method thereof | |
| CN114591607B (en) | PBT composition, and preparation method and application thereof | |
| CN102649872A (en) | Modified PC (Poly Carbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy | |
| CN112745651B (en) | Flame-retardant polycarbonate composition and preparation method and application thereof | |
| CN105419253A (en) | Polybutylene terephthalate composition and preparation method thereof | |
| CN112111138A (en) | Flame-retardant polycarbonate composition and preparation method thereof | |
| CN113527858A (en) | High-strength high-toughness antibacterial mildew-proof flame-retardant PC/ABS alloy material and preparation method thereof | |
| CN112724629B (en) | Polycarbonate composition and preparation method and application thereof | |
| CN114437519A (en) | PBT/PC alloy material and preparation method and application thereof | |
| CN108841172B (en) | Non-reinforced halogen-free flame-retardant polyamide composite material and preparation method thereof | |
| CN114031915A (en) | Stable flame-retardant polycarbonate alloy composition and preparation method and application thereof | |
| CN107573667B (en) | High-temperature-resistant polycarbonate composition and preparation method thereof | |
| CN104693749A (en) | PC/PBT alloy with excellent flame resistance and weather resistance | |
| CN101210106A (en) | Low odor low total carbon emanation PC/ABS alloy and preparing method thereof | |
| CN110105704B (en) | Polyformaldehyde composite material with low formaldehyde emission and preparation method thereof | |
| CN111117184A (en) | High-temperature and high-humidity resistant flame-retardant PC plastic and preparation method and application thereof | |
| EP0204520A2 (en) | Polyetherketone resin composition | |
| CN115627063A (en) | Flame-retardant PBT/PC alloy material and preparation method and application thereof | |
| CN107556724B (en) | High-fluidity high-toughness PC/PET composite material and preparation method thereof | |
| CN105348641A (en) | Calcium carbonate filled flame-retardant polypropylene material and preparation method thereof | |
| CN107573666A (en) | Weather resistant PC/PET alloy and preparation method thereof | |
| CN112029254A (en) | Damp-heat-aging-resistant halogen-free flame-retardant PC/ABS alloy material and preparation method thereof | |
| CN114410027B (en) | PVC/ABS alloy material and application 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 |