CN104059358A - Flame-retardant thermoplastic polyamide composition, and preparation method and application thereof - Google Patents
Flame-retardant thermoplastic polyamide composition, and preparation method and application thereof Download PDFInfo
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- CN104059358A CN104059358A CN201410259469.7A CN201410259469A CN104059358A CN 104059358 A CN104059358 A CN 104059358A CN 201410259469 A CN201410259469 A CN 201410259469A CN 104059358 A CN104059358 A CN 104059358A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
Abstract
The invention discloses a flame-retardant thermoplastic polyamide composition which comprises 25-94% of thermoplastic polyamide resin, 5-20% of red phosphorus flame retardant, 0-50% of reinforcing material and 0.5-5% of adsorbent, wherein the adsorbent is nigrosine. The preparation method comprises the following steps: through a melt blending and extrusion process, adding the thermoplastic polyamide resin, part of all of the reinforcing material and the adsorbent via a main feed inlet, adding the rest of the reinforcing material via a first side feed inlet, and adding the red phosphorus flame retardant via a second side feed inlet; and performing melt blending, cooling, performing air drying, and granulating. According to the invention, the red phosphorus flame-retardant polyamide composition, prepared by adding the nigrosine used as the adsorbent into the polyamide and controlling the nigrosine content, has excellent flame retardancy and electric property, and can effectively reduce the hydrogen phosphide release amount in the injection molding process, reduce the harm to physical fitness of personnel and simultaneously improve the use safety of the material. The flame-retardant thermoplastic polyamide composition is applicable to spare parts of electronic/electrical/electrotechnical products.
Description
Technical field
The present invention relates to polymeric material field, be specifically related to a kind of red phosphorus flame-retardant polyamide thermoplastic compositions and its preparation method and application.
Background technology
Polymeric amide is referred to as nylon, because containing recurring amide radical group-[NHCO]-gain the name on molecular backbone chain, due to the amide group with polarity on molecular structure, makes to form stronger hydrogen bond action between molecular chain, has higher crystallinity, superior mechanical property.Polymeric amide is that output maximum in five large general engineering plastic, kind are maximum, purposes is the widest, a class base resin of high comprehensive performance.
Red phosphorus is as a kind of general halogen-free flame retardants, not only flame retardant properties is good for it, addition is little, physicals on base resin and electric property impact are little, and red phosphorus flame-retardant material due to have when burning the amount of being fuming little compared with halogenated flame retardant, fire retardant can not move to surface, CTI high, thus be subject to the great attention of industry.Red phosphorus flame-retardant polymeric amide has superior mechanical property and electrical property, more and more obtains the favor of electrical engineering and electric apparatus industry manufacturers, and simultaneously due to its higher cost performance, market prospect of the application is boundless.
Because polymeric amide has more polarity amide group, make polymeric amide ratio be easier to water suction, and water-intake rate is higher, if PA6 resin is at 23 DEG C, under 50% humidity condition, water-intake rate can arrive 3%.Red phosphorus flame-retardant polyamide material is in injection moulding process, and due to higher mold temperature, red phosphorus can react with airborne oxygen and water and generate toxic gas-phosphuret-(t)ed hydrogen, some adopts the mould of hot runner especially, its mold temperature is higher, and what have even exceedes 300 DEG C, and the phosphuret-(t)ed hydrogen of its formation is more.Phosphuret-(t)ed hydrogen is a kind of hypertoxic gas, is thrown into the life security that not only directly threatens the mankind in atmosphere, and it spontaneous combustion also more easily occurs, and forming materials employee's life and health is formed to larger threat.
At present, the main method that solves phosphuret-(t)ed hydrogen release And Spread of Solute in the injection moulding of red phosphorus flame-retardant polyamide material is that micro encapsulation processing is carried out in red phosphorus combustion inhibitor surface, avoids contacting of moisture and oxygen and red phosphorus.As patents such as patent CN1775664A, CN101503568B, by red phosphorus being carried out to micro encapsulation processing, form coating layer on red phosphorus surface, protection red phosphorus is not oxidized.But under the strong shearing action of high temperature, screw rod, the coating layer of red phosphorus, inevitably by partial destruction, causes the release of phosphuret-(t)ed hydrogen.
Chinese patent CN 103304997A discloses red phosphorus flame-retardant Reinforced Nylon of a kind of anacidity burn into high electric insulation and preparation method thereof, main by being dried in advance polymeric amide and red phosphorus, adopt and pass into the special expressing techniques such as rare gas element simultaneously, reduction red phosphorus contacts with water and oxygen.The method, is that expressing technique is more loaded down with trivial details on the one hand, and the red phosphorus of while in injection moulding process also inevitable material reacts with water and oxygen.
Patent EP2072566B1 discloses a kind of red phosphorus flame-retardant material of low phosphatization hydrogen release, main by adding high surface area material, as the material such as gac, zeolite, reduces the phosphuret-(t)ed hydrogen burst size of material after extruding.But the method is (as injection moulding) poor effect in the moulding of material later stage, add these high surface area materials simultaneously and can further promote the water-intake rate of nylon, in post-treatment, further strengthen reacting of red phosphorus and water and oxygen.
Disclosed patent is conducive to slow down contacting of red phosphorus and water and oxygen in material above, reduce the corrosion of material, or the phosphuret-(t)ed hydrogen of reduction material in the time of graininess, but in material injection molding process, when material experiences after a shear at high temperature again, the burst size of phosphuret-(t)ed hydrogen is still very high, and moulding personnel are produced compared with major injury, due to red phosphorus hydrolysis and oxidation generation acidic substance, be unfavorable for the safe handling of material simultaneously.
Summary of the invention
The object of the invention is to overcome the deficiency that existing red phosphorus flame-retardant polyamide thermoplastic compositions exists, reduce the burst size of phosphuret-(t)ed hydrogen in forming materials process, alleviate the injury healthy to personnel, promote the safety in utilization of material simultaneously, the flame-proofed thermoplastic daiamid composition of a kind of Halogen, low phosphatization hydrogen release is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned flame-proofed thermoplastic daiamid composition.
The present invention is achieved through the following technical solutions:
A kind of flame-proofed thermoplastic daiamid composition, by weight percentage, comprises following component:
Thermoplastic polyamide resin 25 ~ 94%;
Red phosphorus combustion inhibitor 5 ~ 20%;
Strongthener 0 ~ 50%;
Sorbent material 0.5 ~ 5%;
Wherein, described sorbent material is nigrosine.
Preferably, flame-proofed thermoplastic daiamid composition of the present invention, by weight percentage, comprises following component:
Thermoplastic polyamide resin 50 ~ 75%;
Red phosphorus combustion inhibitor 8 ~ 14%;
Strongthener 10 ~ 35%;
Sorbent material 0.5 ~ 2%.
Thermoplastic polyamide resin of the present invention can carry out condensation polymerization by di-carboxylic acid and diamine and react and obtain or obtained by lactan ring-opening polymerization.
Available di-carboxylic acid comprises the aromatic acids such as the aliphatic dibasic acids such as oxalic acid, succinic acid, hexanodioic acid, nonane diacid, sebacic acid, laurostearic acid, stearic acid and terephthalic acid, phthalic acid, naphthalene diacid, but is not limited to aforementioned di-carboxylic acid.
Available diamine comprises quadrol, butanediamine, hexanediamine, nonamethylene diamine, decamethylene diamine, undecylamine, amino dodecane, cetylamine, stearylamine, Ursol D, mphenylenediamine, O-Phenylene Diamine, 4,4 '-diaminodiphenyl-methane, but be not limited to aforementioned diamine.
Available lactan comprises butyrolactam, Valerolactim, hexanolactam, oenantholactam, spicy inner formyl amine, ninth of the ten Heavenly Stems lactan, caprinolactam, laurolactam, 16 lactan, 18 lactan, but is not limited to aforementioned lactan.
Preferred di-carboxylic acid is succinic acid, hexanodioic acid, terephthalic acid above, and preferred diamine is butanediamine, hexanediamine, Ursol D, and preferred lactan is hexanolactam.
Preferably, thermoplastic polyamide resin of the present invention is selected from one or more the mixture in nylon 6, nylon 66, nylon 46, nylon 6/66, NYLON610, nylon 611, nylon 612, nylon 6T, nylon 9 T.
Red phosphorus combustion inhibitor in the present invention can use known fire retardant.As red phosphorus combustion inhibitor, the microcapsule red phosphorus inflaming retarding master batch of preferably making through the coated red phosphorus of processing of micro encapsulation, its processing mode is to carry out compound coating processing by two kinds in resol, ultrapas formaldehyde resin, trimeric cyanamide cyanogen urea acid resin, epoxy resin, silicone resin, urethane resin, polyacrylic ester, polyacrylamide etc. or two or more resins, and adopt zinc borate simultaneously, one or more inorganic salt in zinc phosphate, copper borate, calcium phosphate, lime borate, Calucium Silicate powder, zinc silicate etc. carry out compound coating processing.The vector resin using is nylon 6, EVA, PE, POE, EPDM or EVA, PE, P0E, EPDM, PP through maleic anhydride, vinylformic acid, acrylate, the modification of glycidyl acrylate graft reaction; Vector resin accounts for 10 60% of red phosphorus flame-retardant masterbatch quality.
Sorbent material of the present invention is nigrosine, nigrosine normally relates to induline and takes one group of black or the grey phenazine dyes (azines) of various forms (water-soluble, oil soluble, alcohol dissolubility), be used in woolen dyed and wool stamp, silk and dye in black and leather, shoe polish, varnish, plastics, stoving lacquer, ink etc. painted, also can be used as micro-dyestuff.By heating oil of mirbane, aniline and aniline hydrochloride and metallic iron and FeCl
3and from the industrial nigrosine that obtains.
Strongthener of the present invention is E glass fibre, B glass fibre, carbon fiber, aromatic polyamide fibre, fibrous magnesium silicate, wollastonite fibre, ceramic fiber, potassium titanate crystal whisker, alkali magnesium sulfate crystal whisker, silicon carbide whisker, aluminium borate whisker or silicon-dioxide, pure aluminium silicate, silicon oxide, calcium carbonate, titanium dioxide, talcum, wollastonite, diatomite, clay, kaolin, globular glass, mica, gypsum, ferric oxide, the powdery such as magnesium oxide and zinc oxide or tabular mineral compound.
Composition of the present invention can optionally comprise other additional compositions, and described additional composition can include but are not limited to, some auxiliary agents such as thermo-stabilizer, processing aid, lubricant, releasing agent, color additives, impact modifying agent and oxidation inhibitor.
The preparation method of flame-proofed thermoplastic daiamid composition of the present invention, comprises the following steps:
Adopt melt blending expressing technique to produce, utilize single screw extrusion machine, twin screw extruder or multiple screw extruder, add thermoplastic polyamide resin, part or all of strongthener, sorbent material from main spout, first side spout adds remaining
Strongthener, second side spout adds red phosphorus combustion inhibitor; After melt blending, through cooling, air-dry and granulation, to obtain final product.
Flame-proofed thermoplastic daiamid composition of the present invention can be by extruding, injection moulding, compression molding are goods, for the component of electronics, electrical equipment, electric product.
The present invention compared with prior art, has following beneficial effect:
The present invention adds nigrosine as sorbent material in polymeric amide, and by controlling the content of nigrosine, the red phosphorus flame-retardant daiamid composition preparing not only has excellent flame retardant properties and electrical property, and can effectively reduce the burst size of phosphuret-(t)ed hydrogen in injection moulding process, alleviate the injury healthy to personnel, promote the safety in utilization of material, simultaneously can the corrosion of lightening material to mould, be suitable for the component of electronics, electrical equipment, electric product.
Embodiment
Further illustrate the present invention below by embodiment, following examples are preferably embodiment of the present invention, but embodiments of the present invention are not subject to the restriction of following embodiment.
Embodiments of the invention adopt following raw material:
PA66 resin: PA66 EPR27, Shen Ma limited-liability company
PA6 resin: PA6 M2800, Meida Nylon Co., Ltd., Xinhui, Guangdong
Red phosphorus combustion inhibitor: RPM440B(red phosphorus content 50%, PA6 is carrier), company limited of lokav morning twilight chemical research institute
Glass: glass ECS301CL-3, Chongqing international matrix material limited-liability company
Nigrosine: TN-870, Orient Chem. Limited, Japan
Carbon black: M717, Cabot
material performance test method:
1. phase ratio creepage tracking index CTI: make 100 × 100 × 3.0mm side plate by injection molding, test according to IEC 60112 standards.
2. flame retardant resistance: make 125 × 13 × 1.6mm by injection molding, test according to UL-94 standard.
3. phosphuret-(t)ed hydrogen burst size test
Required equipment: drying basin (bore 300mm), phosphuret-(t)ed hydrogen detector: (German Dreager production) and stopwatch.
Injection temperature: 290 DEG C, 285 DEG C, 280 DEG C, 265 DEG C, mould: common burning batten mould.The burning batten (comprising the mouth of a river) just having injected is put in drying basin immediately, put together phosphuret-(t)ed hydrogen detector into drying basin simultaneously, press stopwatch and start timing, while observing stopwatch 5min, the reading of phosphuret-(t)ed hydrogen detector.
Reading/burning batten quality (kg) of phosphuret-(t)ed hydrogen burst size=phosphuret-(t)ed hydrogen detector.
[embodiment 1 ~ embodiment 5]
After adding mixing machine to mix polyamide resin, red phosphorus combustion inhibitor, nigrosine and other processing aid according to the material proportion in table 1, add forcing machine from main spout; Strongthener adds forcing machine by side spout.After melt blending, through cooling, air-dry and granulation, performance test is as shown in table 1.
[reference examples 1 ~ reference examples 3]
Except nigrosine is substituted by carbon black, or nigrosine content is reduced to (< 0.5%) or while increasing (> 5.0), other composition proportion, as table 1, is carried out similarly to Example 1, obtain granulation particle, performance test is as shown in table 1.
Component proportioning and the performance test results of the each composition of table 1
As can be seen from Table 1, the present invention by adding the nigrosine of certain content in polymeric amide, and the red phosphorus flame-retardant daiamid composition preparing not only has excellent flame retardant properties and electrical property, and can obviously suppress the burst size of phosphuret-(t)ed hydrogen in injection moulding process.
Claims (8)
1. a flame-proofed thermoplastic daiamid composition, is characterized in that: by weight percentage, comprise following component:
Thermoplastic polyamide resin 25 ~ 94%;
Red phosphorus combustion inhibitor 5 ~ 20%;
Strongthener 0 ~ 50%;
Sorbent material 0.5 ~ 5%;
Wherein, described sorbent material is nigrosine.
2. flame-proofed thermoplastic daiamid composition according to claim 1, is characterized in that: by weight percentage, comprise following component:
Thermoplastic polyamide resin 50 ~ 75%;
Red phosphorus combustion inhibitor 8 ~ 14%;
Strongthener 10 ~ 35%;
Sorbent material 0.5 ~ 2%.
3. flame-proofed thermoplastic daiamid composition according to claim 1 and 2, is characterized in that: described thermoplastic polyamide resin is selected from one or more the mixture in nylon 6, nylon 66, nylon 46, nylon 6/66, NYLON610, nylon 611, nylon 612, nylon 6T, nylon 9 T.
4. flame-proofed thermoplastic daiamid composition according to claim 1 and 2, is characterized in that: described red phosphorus combustion inhibitor is microcapsule red phosphorus inflaming retarding master batch.
5. flame-proofed thermoplastic daiamid composition according to claim 4, it is characterized in that: described microcapsule red phosphorus inflaming retarding master batch is that wherein vector resin accounts for 10 60% of microcapsule red phosphorus inflaming retarding master batch quality taking EVA, the PE of nylon 6, EVA, PE, POE, EPDM or process maleic anhydride, vinylformic acid, acrylate, the modification of glycidyl acrylate graft reaction, P0E, EPDM, PP as vector resin.
6. flame-proofed thermoplastic daiamid composition according to claim 1 and 2, is characterized in that: described strongthener is one or more the mixing in E glass fibre, B glass fibre, carbon fiber, aromatic polyamide fibre, fibrous magnesium silicate, wollastonite fibre, ceramic fiber, potassium titanate crystal whisker, alkali magnesium sulfate crystal whisker, silicon carbide whisker, aluminium borate whisker, silicon-dioxide, pure aluminium silicate, silicon oxide, calcium carbonate, titanium dioxide, talcum, wollastonite, diatomite, clay, kaolin, globular glass, mica, gypsum, ferric oxide, magnesium oxide or zinc oxide.
7. the preparation method of the flame-proofed thermoplastic daiamid composition described in claim 1 ~ 6 any one, is characterized in that: comprise the following steps:
Adopt melt blending expressing technique to produce, utilize single screw extrusion machine, twin screw extruder or multiple screw extruder, add thermoplastic polyamide resin, part or all of strongthener, sorbent material from main spout, the
A side spout adds remaining strongthener, and second side spout adds red phosphorus combustion inhibitor; After melt blending, through cooling, air-dry and granulation, to obtain final product.
8. the application of the flame-proofed thermoplastic daiamid composition described in claim 1 ~ 6 any one in the component of electronics, electrical equipment or electric product.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962076A (en) * | 2015-07-30 | 2015-10-07 | 苏州荣昌复合材料有限公司 | Nylon 66 modified plastic and preparation method thereof |
| CN105038207A (en) * | 2015-06-18 | 2015-11-11 | 颜红兵 | Polyamide enhanced formula for lamp fitting with flame retardancy, high temperature resistance and high luster |
| CN105924119A (en) * | 2016-05-10 | 2016-09-07 | 王跃林 | Space partition board and manufacturing method thereof |
| CN106280426A (en) * | 2016-09-19 | 2017-01-04 | 南京德尔隆工程塑料有限公司 | A kind of false proof characters cut in intaglio laser marking injection PP Pipe Compound and preparation method thereof |
| CN107793749A (en) * | 2017-09-30 | 2018-03-13 | 中广核俊尔新材料有限公司 | A kind of low smell red phosphorus flame-retardant reinforced polyamide material |
| CN107815102A (en) * | 2017-11-01 | 2018-03-20 | 泰山石膏（铜陵）有限公司 | A kind of preparation method of the anhydrite powder composite of nylon 6 of anodizing modified carbon fiber enhancing |
| CN107892810A (en) * | 2017-11-23 | 2018-04-10 | 广东奇德新材料股份有限公司 | Fire-retardant polyamide compoiste material of a kind of low volatilization and preparation method thereof |
| CN109023585A (en) * | 2018-08-03 | 2018-12-18 | 巢湖市渔郎渔具有限公司 | A kind of antibiotic cleaning fishing net and preparation method thereof |
| CN109679335A (en) * | 2018-11-23 | 2019-04-26 | 中广核俊尔新材料有限公司 | A kind of red phosphorus flame-retardant enhancing nylon material and preparation method thereof that low surface is precipitated |
| CN111499922A (en) * | 2020-05-28 | 2020-08-07 | 杭州本松新材料技术股份有限公司 | Red phosphorus flame-retardant system, thermoplastic composition, preparation method and application |
| CN113527877A (en) * | 2020-04-14 | 2021-10-22 | 中蓝晨光化工研究设计院有限公司 | high-CTI-value black red phosphorus flame-retardant reinforced nylon 66 and preparation method thereof |
| CN116285319A (en) * | 2023-05-08 | 2023-06-23 | 厦门博程塑胶材料有限公司 | Environment-friendly halogen-free flame-retardant nylon composite material and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038207A (en) * | 2015-06-18 | 2015-11-11 | 颜红兵 | Polyamide enhanced formula for lamp fitting with flame retardancy, high temperature resistance and high luster |
| CN104962076A (en) * | 2015-07-30 | 2015-10-07 | 苏州荣昌复合材料有限公司 | Nylon 66 modified plastic and preparation method thereof |
| CN105924119A (en) * | 2016-05-10 | 2016-09-07 | 王跃林 | Space partition board and manufacturing method thereof |
| CN106280426A (en) * | 2016-09-19 | 2017-01-04 | 南京德尔隆工程塑料有限公司 | A kind of false proof characters cut in intaglio laser marking injection PP Pipe Compound and preparation method thereof |
| CN107793749A (en) * | 2017-09-30 | 2018-03-13 | 中广核俊尔新材料有限公司 | A kind of low smell red phosphorus flame-retardant reinforced polyamide material |
| CN107815102A (en) * | 2017-11-01 | 2018-03-20 | 泰山石膏（铜陵）有限公司 | A kind of preparation method of the anhydrite powder composite of nylon 6 of anodizing modified carbon fiber enhancing |
| CN107892810A (en) * | 2017-11-23 | 2018-04-10 | 广东奇德新材料股份有限公司 | Fire-retardant polyamide compoiste material of a kind of low volatilization and preparation method thereof |
| CN109023585A (en) * | 2018-08-03 | 2018-12-18 | 巢湖市渔郎渔具有限公司 | A kind of antibiotic cleaning fishing net and preparation method thereof |
| CN109679335A (en) * | 2018-11-23 | 2019-04-26 | 中广核俊尔新材料有限公司 | A kind of red phosphorus flame-retardant enhancing nylon material and preparation method thereof that low surface is precipitated |
| CN113527877A (en) * | 2020-04-14 | 2021-10-22 | 中蓝晨光化工研究设计院有限公司 | high-CTI-value black red phosphorus flame-retardant reinforced nylon 66 and preparation method thereof |
| CN113527877B (en) * | 2020-04-14 | 2023-05-02 | 中蓝晨光化工研究设计院有限公司 | High CTI value black red phosphorus flame-retardant reinforced nylon 66 and preparation method thereof |
| CN111499922A (en) * | 2020-05-28 | 2020-08-07 | 杭州本松新材料技术股份有限公司 | Red phosphorus flame-retardant system, thermoplastic composition, preparation method and application |
| CN111499922B (en) * | 2020-05-28 | 2022-03-08 | 杭州本松新材料技术股份有限公司 | Red phosphorus flame-retardant system, thermoplastic composition, preparation method and application |
| CN116285319A (en) * | 2023-05-08 | 2023-06-23 | 厦门博程塑胶材料有限公司 | Environment-friendly halogen-free flame-retardant nylon composite material and preparation process thereof |
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