CN112724630B - Infrared-transmitting flame-retardant polycarbonate composition and preparation method and application thereof - Google Patents
Infrared-transmitting flame-retardant polycarbonate composition and preparation method and application thereof Download PDFInfo
- Publication number
- CN112724630B CN112724630B CN202011477118.5A CN202011477118A CN112724630B CN 112724630 B CN112724630 B CN 112724630B CN 202011477118 A CN202011477118 A CN 202011477118A CN 112724630 B CN112724630 B CN 112724630B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- polycarbonate composition
- infrared
- retardant polycarbonate
- flame
- 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
- C08K2003/166—Magnesium halide, e.g. magnesium 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
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 relates to an infrared-transmitting flame-retardant polycarbonate composition, and a preparation method and application thereof. The flame-retardant polycarbonate composition which is transparent to infrared rays comprises polycarbonate, magnesium fluoride, calcium sulfate, a complexing agent, a flame retardant, an anti-dripping agent and other processing aids. The flame-retardant polycarbonate composition with infrared transmission provided by the invention has higher infrared transmission rate, lower visible light transmission rate, better toughness and better electric flame-retardant property.
Description
Technical Field
The invention belongs to the field of engineering plastics, and particularly relates to an infrared-transmitting 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. To the requirement that accurate control is realized through the fast propagation to the signal in the intelligence trip, in automobile-used material and electron electrical industry, it is especially important that the shell material has the infrared ray penetration ability that satisfies. 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, the electrical flame retardant safety performance is greatly influenced.
Therefore, it is important to develop a polycarbonate material having excellent electrical flame retardancy while satisfying the requirements of infrared ray transmission and visible light transmission and having excellent toughness to ensure safety.
Disclosure of Invention
The invention aims to overcome the defect or deficiency that the shell material is only black in the prior art, and provides an infrared-transmitting flame-retardant polycarbonate composition. The flame-retardant polycarbonate composition with infrared transmission provided by the invention has higher infrared transmission rate, lower visible light transmission rate, better toughness and better electric flame-retardant property.
Another object of the present invention is to provide a method for preparing the above infrared ray transmitting flame retardant polycarbonate composition.
The invention also aims to provide application of the infrared-transmitting flame-retardant polycarbonate composition in preparation of automotive materials or electronic and electrical equipment.
In order to achieve the purpose, the invention adopts the following technical scheme:
an infrared-transmitting flame-retardant polycarbonate composition comprises the following components in parts by weight:
researches find that white magnesium fluoride and calcium sulfate both have certain infrared transmission effect, and the addition of the magnesium fluoride and the calcium sulfate is expected to lighten the color of a polycarbonate system and improve the infrared transmission rate. However, magnesium fluoride must be added in a large amount to achieve the desired infrared transmittance, and calcium sulfate has a limited effect of improving the infrared transmittance, and cannot achieve the desired infrared transmittance even if added in a large amount. The toughness and the fluidity of a polycarbonate system are obviously deteriorated due to the magnesium fluoride or the calcium sulfate which is added in a large amount; and the dispersibility of the filler has a great influence on the electrical properties, and if the filler is not uniformly dispersed, the electrical properties of the polycarbonate system are obviously deteriorated.
Through multiple researches, the inventor of the invention finds that when magnesium 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 magnesium fluoride and the calcium sulfate, and a good mobile phase is ensured; wherein, the proper amount of magnesium fluoride plays a main role in improving the infrared transmittance, and the proper amount of calcium sulfate plays a main role in reducing the visible light transmittance. Meanwhile, the addition of a small amount of complexing agent can avoid the degradation of metal ions (calcium ions) in a system, prevent the generation of degradation gas marks and water marks during processing and have better appearance quality. In addition, the addition of a proper amount of calcium sulfate enhances the dispersion of magnesium fluoride, the electrical performance is improved under the synergistic effect of the flame retardant, and the electrical performance is also improved along with the increase of the addition amounts of the calcium sulfate and the magnesium fluoride.
The flame-retardant polycarbonate composition with infrared transmission provided by the invention has higher infrared transmission rate, lower visible light transmission rate, better toughness and electrical flame-retardant property.
Preferably, the infrared ray transmitting 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 magnesium fluoride is not higher than 500ppm (for example, 100-500 ppm).
Impurities, such as zinc, are inevitably present in the magnesium fluoride, and an excessive content of impurities will affect the infrared transmission effect (the infrared transmittance will be reduced), and also may 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; an alkylidene-bisphenol; 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, when the thickness of the infrared ray transmitting flame-retardant polycarbonate composition is 2mm, the infrared ray transmittance is more than 45 percent, and the visible light transmittance is not more than 70 percent; GWIT is more than 800 ℃.
The preparation method of the flame-retardant polycarbonate composition transmitting infrared rays comprises the following steps: mixing polycarbonate, magnesium fluoride, calcium sulfate, a complexing agent, a flame retardant, an anti-dripping agent and other processing aids, extruding and granulating to obtain the flame-retardant polycarbonate composition through which infrared rays penetrate.
The application of the infrared-transmitting 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:
the flame-retardant polycarbonate composition with infrared transmission provided by the invention has higher infrared transmission rate and visible light transmission rate, better toughness and electric flame-retardant property, lighter color and better appearance quality.
The preparation method has the advantages of simple process, strong applicability and easy popularization and application.
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:
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;
magnesium fluoride No. 1, magnesium fluoride, Meclin, and impurity zinc content no more than 350 ppm;
magnesium fluoride No. 2, magnesium fluoride, Mecline, and the content of impurity zinc is 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 infrared ray transmitting flame retardant polycarbonate compositions of the examples and comparative examples of the present invention 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.
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.
GWIT: the glow wire performance at 750 ℃ with a thickness of 2.0mm was tested according to the standard IEC 60965-2: 2000.
The preparation process of the infrared ray transmitting flame retardant polycarbonate compositions of the examples and comparative examples of the present invention is as follows: mixing polycarbonate, magnesium fluoride, calcium sulfate, a complexing agent, a flame retardant, an anti-dripping agent and other processing aids (if any), extruding and granulating to obtain the flame-retardant polycarbonate composition.
Examples 1 to 13
This example provides a series of infrared light transmitting flame retardant polycarbonate compositions having the components and amounts shown 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 infrared light transmitting 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 infrared light transmitting 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 infrared ray transmitting flame retardant polycarbonate compositions of each example and comparative example 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 composition provided by the embodiments of the present invention has high infrared transmittance, low visible light transmittance, good fluidity and electrical properties. Wherein, in a certain range, the infrared light transmittance is increased along with the increase of the addition amount of magnesium fluoride, the visible light transmittance is reduced, the fluidity is slightly deteriorated, and the electrical performance is improved; however, if only magnesium fluoride is added (as in comparative example 5), a large amount of magnesium fluoride is added to achieve a high infrared transmittance; but the reduction of the visible light transmittance is not obvious, and the fluidity of the polycarbonate resin is seriously influenced, and in addition, the electrical performance cannot be effectively improved due to the lack of the synergistic dispersion of the magnesium fluoride and the calcium sulfate. Within a certain range, with the increase of the addition amount of calcium sulfate, the infrared light transmittance is increased, the visible light transmittance is reduced, the fluidity is slightly deteriorated, and the electrical performance is improved; however, if only calcium sulfate is added (as in comparative example 6), even a large amount of calcium sulfate is added, a high infrared transmittance cannot be achieved, and only the visible light transmittance can be effectively reduced; in addition, the fluidity of the polycarbonate resin is affected by a large amount of added calcium sulfate, and the electrical properties cannot be effectively improved due to lack of synergistic dispersion of magnesium fluoride and calcium sulfate. In contrast, in comparative example 1, calcium fluoride and calcium sulfate were not added, so that there was no effect of infrared transmission and the visible light transmittance was high; 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 although there was a higher infrared transmittance and a lower visible light transmittance, the PC resin was degraded by the active metals in the magnesium fluoride and calcium sulfate, the fluidity was significantly increased, and the electrical properties were slightly reduced; the comparative example 3 does not add magnesium fluoride, so that the fluidity is good, but the infrared transmittance cannot be ensured, the reduction of the visible light transmittance is limited, and the electrical performance is not obviously improved; comparative example 4 does not add calcium sulfate, and the fluidity is better, but the visible light transmittance is too large, the infrared light transmittance is improved limitedly, and the electrical performance is not improved obviously.
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 can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (10)
1. The flame-retardant polycarbonate composition which is transparent to infrared rays 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 infrared ray transmitting flame retardant polycarbonate composition of claim 1, comprising the following components in parts by weight:
3. the infrared ray transmitting flame retardant polycarbonate composition according to claim 1, wherein the polycarbonate has a weight average molecular weight of more than 40000.
4. The infrared ray transparent flame retardant polycarbonate composition of claim 1, wherein the magnesium fluoride has a zinc impurity content of not more 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 infrared ray transmitting flame retardant polycarbonate composition according to 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 infrared light transmitting, 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 infrared ray transmitting flame retardant polycarbonate composition of claim 1, wherein when the thickness of the flame retardant polycarbonate composition is 2mm, the infrared ray transmittance is not less than 45% and the visible light transmittance is not more than 70%; GWIT is not lower than 800 ℃.
9. The method for preparing an infrared transmitting flame retardant polycarbonate composition of any of claims 1 to 8, comprising the steps of: mixing polycarbonate, magnesium fluoride, calcium sulfate, a complexing agent, a flame retardant, an anti-dripping agent and other processing aids, extruding and granulating to obtain the flame-retardant polycarbonate composition through which infrared rays penetrate.
10. Use of the infrared transmitting flame retardant polycarbonate composition of any of claims 1 to 8 for the preparation of automotive materials or electronic and electrical devices.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011477118.5A CN112724630B (en) | 2020-12-15 | 2020-12-15 | Infrared-transmitting flame-retardant polycarbonate composition and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011477118.5A CN112724630B (en) | 2020-12-15 | 2020-12-15 | Infrared-transmitting flame-retardant polycarbonate composition and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112724630A CN112724630A (en) | 2021-04-30 |
| CN112724630B true CN112724630B (en) | 2022-05-17 |
Family
ID=75602408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011477118.5A Active CN112724630B (en) | 2020-12-15 | 2020-12-15 | Infrared-transmitting flame-retardant polycarbonate composition and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112724630B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115246985B (en) * | 2022-08-23 | 2023-10-17 | 金发科技股份有限公司 | Processing-stable infrared-transmitting white polycarbonate composition and preparation method and application thereof |
| CN115433448B (en) * | 2022-08-31 | 2023-07-18 | 天津金发新材料有限公司 | Polycarbonate composition 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 |
| US20190152197A1 (en) * | 2016-06-15 | 2019-05-23 | Sabic Global Technologies B.V. | Multilayer structures and methods of forming the same |
-
2020
- 2020-12-15 CN CN202011477118.5A patent/CN112724630B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112724630A (en) | 2021-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112724630B (en) | Infrared-transmitting flame-retardant polycarbonate composition and preparation method and application thereof | |
| EP2716712B1 (en) | Polycarbonate resin composition and molded article | |
| EP2970633A1 (en) | Stabilized polymer compositions and methods of making same | |
| CN113999498B (en) | Low-post-shrinkage high-toughness flame-retardant PBT/PC composition, and preparation method and application thereof | |
| WO2016197907A1 (en) | Polycarbonate composition and preparation method therefor | |
| CN108117732B (en) | Halogen-free flame-retardant polycarbonate alloy and preparation method thereof | |
| CN112111138A (en) | Flame-retardant polycarbonate composition and preparation method thereof | |
| CN111171548B (en) | high-CTI (comparative tracking index) and low-temperature super-tough flame-retardant PC (polycarbonate) material and preparation method thereof | |
| CN101104730B (en) | Low-fluorine anti-flaming polycarbonate/styryl resin composition | |
| CN113527858A (en) | High-strength high-toughness antibacterial mildew-proof flame-retardant PC/ABS alloy material and preparation method thereof | |
| CN112745651B (en) | Flame-retardant polycarbonate composition and preparation method and application thereof | |
| WO2023179555A1 (en) | Halogen-free flame-retardant polycarbonate/styrene resin alloy, and preparation method therefor and use thereof | |
| CN112724629B (en) | Polycarbonate composition and preparation method and application thereof | |
| CN104629285A (en) | Halogen-free flame-retardant high toughness modified polycarbonate composition | |
| CN114031915A (en) | Stable flame-retardant polycarbonate alloy composition and preparation method and application thereof | |
| CN104693749A (en) | PC/PBT alloy with excellent flame resistance and weather resistance | |
| CN113637306A (en) | Low-temperature-resistant flame-retardant antistatic PC/PBT alloy and preparation method thereof | |
| CN111117184A (en) | High-temperature and high-humidity resistant flame-retardant PC plastic and preparation method and application thereof | |
| CN110951236B (en) | Laser direct forming material based on polyphenyl ether and preparation method thereof | |
| WO2022057206A1 (en) | Polycarbonate alloy composition, preparation method therefor and use thereof | |
| CN110105704B (en) | Polyformaldehyde composite material with low formaldehyde emission and preparation method thereof | |
| CN111303604B (en) | Polycarbonate/polyethylene terephthalate-1, 4-cyclohexanedimethanol ester alloy material and preparation method thereof | |
| CN114539758A (en) | Halogen-free flame-retardant PC/ABS composite material and preparation method thereof | |
| CN112029254A (en) | Damp-heat-aging-resistant halogen-free flame-retardant PC/ABS alloy material and preparation method thereof | |
| KR20040065078A (en) | Flame retardant polypropylene resin composition with excellent weatherability |
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 |