CN113045892B - Flame-retardant nylon 66 material and preparation method thereof - Google Patents
Flame-retardant nylon 66 material and preparation method thereof Download PDFInfo
- Publication number
- CN113045892B CN113045892B CN201911384079.1A CN201911384079A CN113045892B CN 113045892 B CN113045892 B CN 113045892B CN 201911384079 A CN201911384079 A CN 201911384079A CN 113045892 B CN113045892 B CN 113045892B
- Authority
- CN
- China
- Prior art keywords
- parts
- nylon
- temperature
- magnesium hydroxide
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
- C08K5/1539—Cyclic anhydrides
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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 discloses a flame-retardant nylon 66 material and a preparation method thereof, wherein the flame-retardant nylon 66 material is prepared from the following components in parts by weight: nylon 66100 parts; 5-10 parts of magnesium hydroxide; 1-3 parts of cyclopentane tetracarboxylic dianhydride; 10980.3-0.5 part of antioxidant; 6260.3-0.5% of antioxidant; 0.5-1 part of lubricant. According to the invention, cyclopentane tetracarboxylic dianhydride is used to increase the dispersibility of magnesium hydroxide, the interfacial strength of magnesium hydroxide and nylon 66 is enhanced, and excellent flame retardant capability can be achieved when the addition amount of magnesium hydroxide is only 5-10 parts. The nylon 66 composition of the invention has excellent mechanical properties, especially strength and impact resistance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a flame-retardant nylon 66 material and a preparation method thereof.
Background
Nylon is a common name for polyamide resins, which is a generic name for a large class of polymers, with nylon 66 and nylon 6 yields of over 90%. The nylon resin has the advantages of high mechanical strength, good toughness, fatigue resistance, self-lubricating property, small friction coefficient, wear resistance, heat resistance (long-term use at 100 ℃), easy modification and forming and the like, has good comprehensive performance and is widely applied.
Unmodified nylon has poor flame retardant performance, the vertical combustion of the unmodified nylon can only reach UL 94V-2 level, the oxygen index is about 24, the unmodified nylon drips in the combustion process, and the unmodified nylon belongs to a flammable material and is very easy to cause fire in the use process. Especially in the field of electronic products, the fire caused by nylon causes countless fires and causes great loss, so that the flame retardant modification of nylon is a subject of common attention and attack in academic and industrial fields at present.
Aluminum hydroxide and magnesium hydroxide are one of the most main varieties of the current inorganic environment-friendly flame retardants, and the proportion of the aluminum hydroxide and the magnesium hydroxide in the total consumption of the flame retardants is always kept above 40%. They have three functions of flame retarding, smoke abatement and filling, are cheaper than halogen and phosphorus flame retarding systems, are nonvolatile, nontoxic and can generate a synergistic flame retarding effect with various substances, and are known as pollution-free inorganic flame retardants.
The aluminum hydroxide can be dehydrated by heating at 230-330 ℃, and is not suitable for nylon 66 resin matrix with higher processing temperature. The magnesium hydroxide has strong polarity, the particle surface is positively charged, secondary agglomeration is easy to form, and the hydrophilicity of the magnesium hydroxide enables the dried product to still contain moisture. The direct addition of the polymer is not favorable for dispersion in a high polymer material, is easy to generate gaps with a high polymer interface, and has poor compatibility. Modification is required to improve the surface activity of the particles, to improve the dispersibility of the powder, to improve the compatibility with the polymer material, and to improve the flame retardant properties of magnesium hydroxide.
Disclosure of Invention
The invention aims to provide a flame-retardant nylon 66 material and a preparation method thereof, and aims to solve the problems in the prior art.
The purpose of the invention is realized by the following technical scheme:
the flame-retardant nylon 66 material is prepared from the following components in parts by weight:
further, the melt index of the nylon 66 under the conditions of 270 ℃ and 2016KG is 8-12g/10 min.
In a further scheme, the particle size of the magnesium hydroxide is 6000-8000 meshes.
In a further scheme, the cyclopentane tetracarboxylic dianhydride is analytically pure, and the purity is higher than 97%.
In a further aspect, the lubricant is oleamide.
The invention also aims to provide a preparation method of the flame-retardant nylon 66 material, which comprises the following steps:
(1) adding 5-10 parts of magnesium hydroxide, 1-3 parts of cyclopentanetetracarboxylic dianhydride and 0.5-1 part of lubricant into a mixer, setting the temperature at 40-50 ℃, setting the rotating speed at 300-; the higher temperature can melt the oleamide, so that the cyclopentane tetracarboxylic dianhydride can be uniformly attached to the surface of the magnesium hydroxide, and the composition can be plasticized uniformly during melt extrusion;
(2) adding 100 parts of nylon 66, 0.3-0.5 part of antioxidant 1098 and 0.3-0.5 part of antioxidant 626 into the premixed material in the step (1), mixing at normal temperature for 1-2 minutes at 100 revolutions/min to obtain a mixed material;
(3) Adding the mixed material from a feed inlet of a double-screw extruder, extruding and granulating to obtain the flame-retardant nylon 66 material. Preferably, the temperature of the first zone of the double-screw extruder is 200-230 ℃, the temperature of the second zone is 240-250 ℃, the temperature of the third zone is 250-260 ℃, the temperature of the fourth zone is 260-270 ℃, the temperature of the fifth zone is 270-280 ℃ and the temperature of the sixth zone is 270-280 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, cyclopentane tetracarboxylic dianhydride is used to increase the dispersibility of magnesium hydroxide, the interfacial strength of magnesium hydroxide and nylon 66 is enhanced, and excellent flame retardant capability can be achieved when the addition amount of magnesium hydroxide is only 5-10 parts.
(2) In the preparation process, firstly, the magnesium hydroxide, the cyclopentane tetracarboxylic dianhydride and the lubricant oleamide are mixed at a higher temperature, the higher temperature can melt the oleamide, and the cyclopentane tetracarboxylic dianhydride can be uniformly attached to the surface of the magnesium hydroxide, so that the composition can be uniformly plasticized during melt extrusion, and a product with excellent performance can be prepared.
(3) The nylon 66 composition prepared by the invention has excellent mechanical properties, especially strength and impact resistance.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The types and suppliers of the reagents used in this example were as follows:
nylon 66 was purchased from Hibiscus Marco under the brand EPR27, melt index 10.8g/10 min;
the magnesium hydroxide is purchased from new magnesium material science and technology limited of Suzhou city under the trade name ZH-H7, the content of the magnesium hydroxide is more than 96 percent, and the particle size is 8000 meshes.
The cyclopentane tetracarboxylic dianhydride is purchased from Taishiai (Shanghai) chemical industry development limited company, and is analytically pure, and the purity is more than 97%.
The lubricant is selected from oleamide purchased from Haimen Hualong oil auxiliary agent factory, white powder, melting point of 72-82 deg.C, and amide content of more than 99.9%.
The reagents are provided only for illustrating the sources and components of the reagents used in the experiments of the present invention, so as to be fully disclosed, and do not indicate that the present invention cannot be realized by using other reagents of the same type or other reagents supplied by other suppliers.
Example 1
10 parts of magnesium hydroxide, 3 parts of cyclopentanetetracarboxylic dianhydride and 1 part of oleamide are added into a mixer, the temperature is set at 50 ℃, the rotating speed is 500 r/min, and the mixture is mixed for 5 minutes. After the temperature is reduced to the normal temperature, 100 parts of nylon 66, 0.5 part of antioxidant 1098 and 0.5 part of antioxidant 626 are added and mixed for 2 minutes at the normal temperature at 200 r/min.
And adding the mixed materials from a feed inlet of a double-screw extruder, extruding and granulating. The first zone temperature of the twin-screw extruder is 230 ℃, the second zone temperature is 250 ℃, the third zone temperature is 260 ℃, the fourth zone temperature is 270 ℃, the fifth zone temperature is 280 ℃ and the sixth zone temperature is 280 ℃.
Example 2
5 parts of magnesium hydroxide, 1 part of cyclopentanetetracarboxylic dianhydride and 0.5 part of oleamide are added into a mixer, the temperature is set at 40 ℃, the rotating speed is 300 r/min, and the mixture is mixed for 3 minutes. After the temperature is reduced to the normal temperature, 100 parts of nylon 66, 0.3 part of antioxidant 1098 and 0.3 part of antioxidant 626 are added and mixed for 1 minute at the normal temperature at 100 revolutions/min.
And adding the mixed materials from a feed inlet of a double-screw extruder, extruding and granulating. The first zone temperature of the twin-screw extruder is 200 ℃, the second zone temperature is 240 ℃, the third zone temperature is 250 ℃, the fourth zone temperature is 260 ℃, the fifth zone temperature is 270 ℃ and the sixth zone temperature is 270 ℃.
Example 3
6 parts of magnesium hydroxide, 2 parts of cyclopentanetetracarboxylic dianhydride and 0.8 part of oleamide are added into a mixer, the temperature is set to 45 ℃, the rotating speed is 400 r/min, and the mixture is mixed for 4 minutes. After the temperature is reduced to the normal temperature, 100 parts of nylon 66, 0.4 part of antioxidant 1098 and 0.4 part of antioxidant 626 are added and mixed for 2 minutes at the normal temperature at 150 r/min.
And adding the mixed materials from a feed inlet of a double-screw extruder, extruding and granulating. The first zone temperature of the twin-screw extruder was 220 ℃, the second zone temperature was 250 ℃, the third zone temperature was 260 ℃, the fourth zone temperature was 270 ℃, the fifth zone temperature was 280 ℃ and the sixth zone temperature was 280 ℃.
Example 4
Adding 8 parts of magnesium hydroxide, 2 parts of cyclopentane tetracarboxylic dianhydride and 0.8 part of oleamide into a mixer, setting the temperature at 45 ℃, rotating speed at 400 r/min, and mixing for 4 minutes. After the temperature is reduced to the normal temperature, 100 parts of nylon 66, 0.4 part of antioxidant 1098, 0.4 part of antioxidant 626 are added and mixed for 1 minute at the normal temperature at 150 r/min.
And adding the mixed materials from a feed inlet of a double-screw extruder, extruding and granulating. The first zone temperature of the twin-screw extruder is 210 ℃, the second zone temperature is 250 ℃, the third zone temperature is 260 ℃, the fourth zone temperature is 270 ℃, the fifth zone temperature is 280 ℃ and the sixth zone temperature is 280 ℃.
Comparative example 1
8 parts of magnesium hydroxide and 0.8 part of oleamide are added into a mixer, the temperature is set to 45 ℃, the rotating speed is 400 r/min, and the mixture is mixed for 4 minutes. After the temperature is reduced to the normal temperature, 100 parts of nylon 66, 0.4 part of antioxidant 1098, 0.4 part of antioxidant 626 are added and mixed for 1 minute at the normal temperature at 150 r/min.
And adding the mixed materials from a feed inlet of a double-screw extruder, extruding and granulating. The first zone temperature of the twin-screw extruder is 210 ℃, the second zone temperature is 250 ℃, the third zone temperature is 260 ℃, the fourth zone temperature is 270 ℃, the fifth zone temperature is 280 ℃ and the sixth zone temperature is 280 ℃.
Comparative example 2
8 parts of magnesium hydroxide, 2 parts of KH550 and 0.8 part of oleamide are added into a mixer, the temperature is set to 45 ℃, the rotating speed is 400 r/min, and the mixture is mixed for 4 minutes. After the temperature is reduced to the normal temperature, 100 parts of nylon 66, 0.4 part of antioxidant 1098, 0.4 part of antioxidant 626 are added and mixed for 1 minute at the normal temperature at 150 r/min.
And adding the mixed materials from a feed inlet of a double-screw extruder, extruding and granulating. The first zone temperature of the twin-screw extruder is 210 ℃, the second zone temperature is 250 ℃, the third zone temperature is 260 ℃, the fourth zone temperature is 270 ℃, the fifth zone temperature is 280 ℃ and the sixth zone temperature is 280 ℃.
Comparative example 3
8 parts of magnesium hydroxide, 2 parts of KH560 and 0.8 part of oleamide are added into a mixer, the temperature is set at 45 ℃, the rotating speed is 400 r/min, and the mixture is mixed for 4 minutes. After the temperature is reduced to the normal temperature, 100 parts of nylon 66, 0.4 part of antioxidant 1098, 0.4 part of antioxidant 626 are added and mixed for 1 minute at the normal temperature at 150 r/min.
And adding the mixed materials from a feed inlet of a double-screw extruder, extruding and granulating. The first zone temperature of the twin-screw extruder is 210 ℃, the second zone temperature is 250 ℃, the third zone temperature is 260 ℃, the fourth zone temperature is 270 ℃, the fifth zone temperature is 280 ℃ and the sixth zone temperature is 280 ℃.
The mechanical property test method comprises the following steps:
the compositions prepared according to the invention were injection molded using ASTM standards. The spline dimensions (length × width × thickness) are: the sample strip for testing the tensile strength and the bending strength is a dumbbell shape, and is 170mm multiplied by 13mm multiplied by 3.2 mm; the cantilever beam notch impact strength test sample strip is 127mm multiplied by 13mm multiplied by 3.2mm, the V-shaped notch is 1/5 in depth;
tensile strength was measured according to ASTM D638, tensile speed 5 mm/min;
flexural strength was tested according to ASTM D790 at a flexural speed of 1.25 mm/min;
notched izod impact performance was tested according to ASTM D256;
the flame retardant property is tested according to UL-94 standard, and the thickness of a sample strip is 1.6 mm;
The performance tests of the products prepared in the examples and comparative examples are shown in table 1 below:
TABLE 1 Performance test data for products prepared in the examples and comparative examples
From the table, the invention can be seen that the cyclopentane tetracarboxylic dianhydride is used to increase the dispersibility of magnesium hydroxide, enhance the interfacial strength of magnesium hydroxide and nylon 66, and still have excellent flame retardant capability when the addition amount of magnesium hydroxide is only 5-10 parts. The nylon 66 composition of the invention has excellent mechanical properties, especially strength and impact resistance.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. A flame-retardant nylon 66 material is characterized in that: the composition is prepared from the following components in parts by weight:
Nylon 66100 parts;
5-10 parts of magnesium hydroxide;
1-3 parts of cyclopentane tetracarboxylic dianhydride;
10980.3-0.5 part of antioxidant;
6260.3-0.5% of antioxidant;
0.5-1 part of lubricant;
the particle size of the magnesium hydroxide is 6000-; the lubricant is oleamide;
when the flame-retardant nylon 66 material is prepared, firstly, 5-10 parts of magnesium hydroxide, 1-3 parts of cyclopentane tetracarboxylic dianhydride and 0.5-1 part of lubricant are uniformly mixed at the temperature of 40-50 ℃, and then the temperature is reduced to the normal temperature to obtain a premixed material.
2. The flame retardant nylon 66 material of claim 1, wherein: the melt index of the nylon 66 under the conditions of 270 ℃ and 2016KG is 8-12g/10 min.
3. The flame retardant nylon 66 material of claim 1, wherein: the cyclopentane tetracarboxylic dianhydride is analytically pure, and the purity is higher than 97%.
4. A method for preparing a flame retardant nylon 66 material as claimed in any one of claims 1-3, wherein: which comprises the following steps:
(1) adding 5-10 parts of magnesium hydroxide, 1-3 parts of cyclopentanetetracarboxylic dianhydride and 0.5-1 part of lubricant into a mixer, mixing, and cooling to normal temperature to obtain a premixed material;
(2) Adding 100 parts of nylon 66, 0.3-0.5 part of antioxidant 1098 and 0.3-0.5 part of antioxidant 626 into the premixed material in the step (1), and mixing at normal temperature to obtain a mixed material;
(3) adding the mixed material from a feed inlet of a double-screw extruder, extruding and granulating to obtain the flame-retardant nylon 66 material.
5. The method of claim 4, wherein: in the step (1), the mixing temperature is 40-50 ℃, the rotation speed of the mixer is 300-500 r/min, and the mixing time is 3-5 minutes.
6. The method of claim 4, wherein: in the step (2), the mixing time is 1-2 minutes, and the rotation speed of the mixer is 100-200 rpm.
7. The method of claim 4, wherein: in the step (3), the temperature of the first zone of the twin-screw extruder is 200-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911384079.1A CN113045892B (en) | 2019-12-28 | 2019-12-28 | Flame-retardant nylon 66 material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911384079.1A CN113045892B (en) | 2019-12-28 | 2019-12-28 | Flame-retardant nylon 66 material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113045892A CN113045892A (en) | 2021-06-29 |
| CN113045892B true CN113045892B (en) | 2022-06-28 |
Family
ID=76507075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911384079.1A Active CN113045892B (en) | 2019-12-28 | 2019-12-28 | Flame-retardant nylon 66 material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113045892B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116694072B (en) * | 2023-07-13 | 2023-11-28 | 苏州优利金新材料有限公司 | High-flame-retardance nylon composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787290A (en) * | 2010-02-11 | 2010-07-28 | 东华大学 | Method for preparing polyimide intercalated grafted magnesium hydroxide flame retardant |
| CN110256825A (en) * | 2019-07-17 | 2019-09-20 | 苏州和记荣达新材料有限公司 | A kind of fiberglass reinforced fire retardant PET composite material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2002952373A0 (en) * | 2002-10-31 | 2002-11-14 | Commonwealth Scientific And Industrial Research Organisation | Fire resistant material |
| US20060019102A1 (en) * | 2004-07-26 | 2006-01-26 | Kuppsuamy Kanakarajan | Flame-retardant halogen-free polyimide films useful as thermal insulation in aircraft applications and methods relating thereto |
-
2019
- 2019-12-28 CN CN201911384079.1A patent/CN113045892B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101787290A (en) * | 2010-02-11 | 2010-07-28 | 东华大学 | Method for preparing polyimide intercalated grafted magnesium hydroxide flame retardant |
| CN110256825A (en) * | 2019-07-17 | 2019-09-20 | 苏州和记荣达新材料有限公司 | A kind of fiberglass reinforced fire retardant PET composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113045892A (en) | 2021-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101429331A (en) | High-impact resistant halogen-free flame-proof polycarbonate and vinyl cyanide-butadiene-styrene resin alloy and method of producing the same | |
| CN110540750B (en) | Flame-retardant nylon 66 composite material and preparation method thereof | |
| CN107955368B (en) | Heat-conducting nylon with improved heat resistance and preparation method thereof | |
| CN109957240B (en) | Thermoplastic halogen-free low-phosphorus flame-retardant reinforced bio-based PA56 and PA66 composite material and preparation method thereof | |
| CN102516738A (en) | Halogen-free flame-retardant and cold-resistant PC/ABS (Poly Carbonate/Acrylonitrile Butadiene Styrene) material and preparation method thereof | |
| CN110591350B (en) | Smoke-inhibiting polyamide composition and preparation method thereof | |
| CN107418201B (en) | Efficient halogen-free flame-retardant reinforced nylon composite material and preparation method thereof | |
| CN1990533A (en) | Halogen-free flame-proof toughening polypropylene composition and preparation process thereof | |
| CN102911485B (en) | Flame-retardant chain-extended polybutylene terephthalate composition and preparation method thereof | |
| CN101486824B (en) | Preparation of low temperature resistant environment friendly flame-retardant high impact resistance polystyrene composition | |
| CN109957241B (en) | Thermoplastic flame-retardant reinforced bio-based PA56 and PA66 composite material and preparation method thereof | |
| CN104725797B (en) | Method for preparing flame-retardant plastic composite material | |
| CN110791049B (en) | Flame-retardant reinforced polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN102702612B (en) | High-flow precipitation-resistant halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN113045892B (en) | Flame-retardant nylon 66 material and preparation method thereof | |
| CN109957238B (en) | Thermoplastic flame-retardant bio-based PA56 and PA66 composite material and preparation method thereof | |
| CN110643167B (en) | Flame-retardant reinforced polyphenyl ether/polyamide 66 composition and preparation method thereof | |
| CN110698852B (en) | Flame-retardant reinforced polyamide 6/polyphenyl ether composition and preparation method thereof | |
| CN110776729B (en) | Flame-retardant polyphenyl ether/high impact polystyrene composition and preparation method thereof | |
| CN109957243A (en) | A kind of thermoplastic halogen-free flame retarding biology base PA56 and PA66 composite material and preparation method | |
| CN107446338A (en) | A kind of high-glowing-filament-temperature flame-retardancy enhancing PPO/PPS composites and preparation method thereof | |
| CN110724374B (en) | Flame-retardant polyphenyl ether/polyamide 66 composition and preparation method thereof | |
| CN114133691A (en) | Halogen-free flame-retardant antibacterial ABS material and preparation method thereof | |
| CN108795033A (en) | A kind of Flameproof polyamide 5X compositions and preparation method thereof having compared with high fluidity | |
| CN105504741A (en) | Halogen-free flame-retardant basalt-fiber-reinforced polycarbonate alloy material 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 |