CN106519295A - Novel phosphorus-based flame retardant and halogen-free intumescent anti-flaming ABS (Acrylonitrile Butadiene Styrene) resin containing same - Google Patents
Novel phosphorus-based flame retardant and halogen-free intumescent anti-flaming ABS (Acrylonitrile Butadiene Styrene) resin containing same Download PDFInfo
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- CN106519295A CN106519295A CN201610846352.8A CN201610846352A CN106519295A CN 106519295 A CN106519295 A CN 106519295A CN 201610846352 A CN201610846352 A CN 201610846352A CN 106519295 A CN106519295 A CN 106519295A
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/304—Aromatic acids (P-C aromatic linkage)
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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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
- C08L2201/02—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
-
- 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 relates to a novel phosphorus-based flame retardant and halogen-free intumescent anti-flaming ABS (Acrylonitrile Butadiene Styrene) resin containing the same. Organic phosphinate (2-carboxyethyl phenyl melamine phosphinate) is selected as a main body of the flame retardant, the novel phosphorus-based flame retardant has the advantages of white color, less addition amount, good mechanical performance, low smoke density, good flame-retardant performance and the like, and the high-efficiency flame-retardant effect can be obtained in both condensed phase and gas phase; meanwhile, polyamide 66, poly terephthaloyl ethylene diamine and the like are added as charring agents, so that charring of the ABS resin in combustion is promoted; meanwhile, synergistic agents-organic modified montmorillonoid, rare-earth metal oxide and the like are also added, so that the flame-retardant effect is enhanced; the influence on mechanical property of the halogen-free intumescent anti-flaming ABS resin is smaller while higher flame-retardant level is obtained.
Description
Technical field
The invention belongs to environment-friendly flame-resistant ABS resin technical field, is related to phosphorus flame retardant, a kind of especially 2- carboxyethyls benzene
Base phosphinic acid compound the phosphorus flame retardant of synthesis and the halogen-free expanded flame-retardant ABS resin comprising the fire retardant with melamine salt.
Background technology
ABS resin is general thermoplastic engineering plastic.Be by acrylonitrile, butadiene and styrene terpolymer formed it is many
Phase block copolymer.With higher impact strength, good processing characteristics and chemical stability, type is readily molded into, is made
Product are rich in gloss, and have toughness and flexibility concurrently, are widely used in auto industry, electronic apparatus industry, light industry household electrical appliances, weave and build
The field such as build.China is the consumption big country of ABS resin, accounts for the 60% of world's aggregate consumption, especially in recent years electronic apparatus and
The fast development of automobile industry so that China quickly increases to the demand of ABS.But ABS is a kind of inflammable high polymer, its pole
Limited oxygen index only has 18% or so.A large amount of black smokes are produced during burning, continue to burning after fire.Which greatly limits the wide of ABS
General use.
For a long time, the fire-retardant of ABS mainly uses halide-containing.Wherein decabromodiphenyl oxide, tetrabromobisphenol A, eight
The bromide fire retardants such as bromo-ether are best to its flame retardant effect.But these halide-containings easily decompose generation hydrogen halides in burning
Gas simultaneously discharges the noxious substances such as dioxin and dibenzofuran, endangers healthy, pollutes environment.As various countries are to fire-retardant
The continuous improvement of the environmental requirement of product, halogenated flame retardant will be eliminated.
The halogen-free flame retardants of ABS mainly has based on metal hydroxidess, phosphorus flame retardant, nitrogenated flame retardant and phosphorus, nitrogen
Expansion type flame retardant.Metal hydroxidess flame retarding efficiency is not high, can be only achieved preferable fire-retardant effect when only adding more than 60%
Really, but its a large amount of addition substantially reduces can the mechanical property of ABS, it is impossible to meet application requirement.The fire-retardant effect of phosphorus flame retardant
Rate is higher, but heat stability is not good enough, and with ABS poor compatibilities；Due to not hydroxyl in ABS resin, when using at phosphonium flame retardant
During reason, charring layer during burning, is hardly formed, fire retardation is not obvious.Traditional expansion type flame retardant is to the fire-retardant effect of ABS resin
Rate is not high, and addition is larger, the poor compatibility with ABS resin, and hygroscopicity is strong.Therefore traditional Intumescent Retardant System is carried out
Improvement is the important research direction of expandable flame retardant ABS resin.
Phosphinate flame retardant is the phosphorus flame retardant developed in recent years, with flame retarding efficiency height, Halogen, it is nontoxic, do not move
The advantages of shifting, can be used for the fire-retardant of various macromolecular materials such as polyester, PA, acrylonitrile butadiene styrene plastic (ABS).Its
Obtained flame retardant products have the advantages that density is low, fire retardant addition is few, mechanical property is good, color and luster is good, smoke density is relatively low.Mesh
Front report and be dialkyl phosphinic acid salt using more phosphinate flame retardant, but its complex manufacturing is relatively costly, greatly
Many dependence on import.
The content of the invention
The present invention is exactly to provide a kind of Halogen, efficient, expansion type flame-retarding to solve the problems, such as above-mentioned flame-proof ABS
Compound system carrys out flame-proof ABS resin.
To achieve these goals, the technical scheme is that：
A kind of new phosphorus flame retardant, entitled 2- carboxyethyl phenyl phosphinic acids melamine salt, synthetic route is：
Preparation method is：By 2- ethoxy phenyl hypophosphorous acid and tripolycyanamide in molar ratio 1：1 mixing, water is solvent, control
70～90 DEG C of reaction temperature processed, reacts 3～5h, product washing, be dried after white solid powder is 2- carboxyethyl phenyls time phosphine
Sour melamine salt.
A kind of halogen-free expanded flame-retardant ABS resin comprising above-mentioned phosphorus flame retardant, its component and weight percentage are：
And, described ABS resin is one butadiene of acrylonitrile, one styrene copolymer, is molded rank, and proportion is
1.05g/cm3。
And, described auxiliary flame retardant is nylon66 fiber, poly- p-phenylene ethene diamine, organic modification montmonrillonite, rare earth
The mixture of one or more of metal-oxide, polyphosphoric acid amine, melamine cyanurate.
And, described antioxidant is the compound of irgasfos 168 and antioxidant 1076, and its mass ratio is 1:1.
And, described processing aid is white mineral oil.
A kind of preparation method of above-mentioned halogen-free expanded flame-retardant ABS resin, comprises the following steps:
(1) each component is weighed according to each component percentage by weight, and dry 4 hours in 80 DEG C of convection oven；
(2) by phosphorus flame retardant, auxiliary flame retardant, in high speed material machine, mix homogeneously obtains compound I；
(3) compound I, ABS resin, antioxidant, processing aid input high speed mixer are mixed again, obtains compound
Ⅱ；
(4) double screw extruder engine speed 50r/min, one section of temperature are adjusted：185 DEG C, two-stage nitration temperature：190 DEG C, three sections
Temperature：190 DEG C, four sections of section temperature：185 DEG C, head temperature：180 DEG C, II Jing double screw extruder melting extrusions of compound are made
Grain, obtains halogen-free expanded flame-retardant ABS resin.
Advantages of the present invention and technique effect are as follows：
1st, a kind of halogen-free expanded flame-retardant ABS resin of the invention, from organic secondary phosphine acid salt (2- carboxyethyl phenyl phosphinic acids
Melamine salt) as the main body of fire retardant, with color it is white, addition is few, good mechanical property, smoke density are low, fire resistance is good
The advantages of, highly effective flame-retardant effect can be played in condensed phase and gas phase.Add the conducts such as nylon66 fiber, poly- p-phenylene ethene diamine simultaneously
Carbon forming agent, promotes ABS resin aflame into charcoal.Add synergist simultaneously again：Organic modification montmonrillonite, rare earth metal oxygen
Compound etc., strengthens flame retardant effect.While obtaining compared with high fire-retardance rank, the impact to its mechanical property is less.
2nd, the phosphinate flame retardant of present invention synthesis not only has beyond phosphinate flame retardant traditional advantages, also has
The advantages of synthetic method is simple, heat stability is high；And nitrogenated flame retardant tripolycyanamide is introduced in phosphinate flame retardant,
Phosphorus phosphorus-nitrogen coordinated fire-retardant effect can be caused, the effect of expandable flame retardant is reached.
Description of the drawings
Fig. 1 is 2- carboxyethyl phenyl phosphinic acid melamine salts (CEPPAME) and 2- ethoxys phenyl hypophosphorous acid (CEPPA)
Infrared spectrum；
1H-NMR spectrograms of the Fig. 2 for 2- carboxyethyl phenyl phosphinic acid melamine salts (CEPPAME)；
Fig. 3 is the infrared spectrogram that laboratory makes PETA by oneself.
Specific embodiment
New phosphorus flame retardant of the present invention and halogen-free expandable are further illustrated by embodiment below in conjunction with the accompanying drawings
Flame-proof ABS resin.
Embodiment 1
The synthetic method of 2- carboxyethyl phenyl phosphinic acid melamine salts
In equipped with mechanical agitation, thermometer, the 1000mL flasks of reflux condensing tube, add 23.5g's (0.11mol)
CEPPA and 400mL distilled water, after stirring is completely dissolved which, then adds the melamine of 12.6g (0.1mol) again in flask
Amine is 80 DEG C with 500mL distilled water controlling reaction temperature, response time 4h.Question response terminates rear cold filtration, anti-with distilled water
Multiple washing and filtering, obtains white solid powder CEPPAME in 80 DEG C of forced air drying 12h, and yield is 86%.
Fig. 1 is the infrared spectrogram of product CEPPAME of CEPPA and CEPPA and ME.The wherein feature of CEPPA
Peak is：1141cm-1For the stretching vibration peak of P=O, 1241cm-1For the stretching vibration peak of P-Ar, 1426cm-1、1485cm-1With
1592cm-1For the characteristic peak of phenyl ring, 2308cm-1For the characteristic peak of P-OH, 3040cm-1For the stretching vibration peak of-OH in-COOH,
1734cm-1For the stretching vibration peak of C=O.It is known that CEPPA contains 2 reactive functional groups：P-OH and-COOH, in spy
Determine aminating reaction can occur with aminated compoundss under reaction condition.After CEPPA reacts to form CEPPAME with ME, P-OH's
Characteristic peak disappears, and illustrates that ME and P-OH there occurs reaction；And in 3359cm-1And 3142cm-1There is-NH2 antisymmetry with symmetrical suction
Receive peak, 1504cm-1And 802cm-1There is the characteristic peak of-C=N in triazine ring, show that CEPPA and ME has occurred that reaction, it is raw
Into target product.
Fig. 2 is CEPPAME nucleus magnetic hydrogen spectrum analysis of spectra, it can be seen that chemical shift δ=3.70 are water peak, and δ=2.5 are molten
Agent peak, the peak (δ=7.75～7.39) at a, b are benzene ring hydrogen, and the peak (δ=7.2) at c is on tripolycyanamide primary amino radical
Hydrogen, it is-CH adjacent with P that the peak (δ=2.33～2.23) at d is corresponding2- hydrogen, the peak (1.86～1.75) at e is corresponding
It is-CH adjacent with-C=O2- hydrogen, the peak (δ=1.24) at c be active hydrogen.Following table is CEPPAME salt1The change of H-NMR
Displacement study and corresponding peak area, can be inferred that by table and have synthesized target product CEPPAME, and CEPPA and ME is with thing
The ratio 1 of the amount of matter:1 is reacted.
CEPPAME salt1The chemical shift of H-NMR and corresponding peak area
Embodiment 2
A kind of halogen-free expanded flame-retardant ABS resin, by weight percentage including following components:
Described antioxidant is the compound of irgasfos 168 and antioxidant 1076, and its mass ratio is 1:1.
A kind of preparation method of halogen-free expanded flame-retardant ABS resin, comprises the following steps:
(1) each material is weighed according to above-mentioned percentage by weight, and dry 4 hours in 80 DEG C of convection oven.
(2) CEPPAME, OMMT are mixed two minutes in high speed mixer, obtains compound I.
(3) compound I, ABS resin, antioxidant, white mineral oil input high speed mixer are mixed two minutes again, is mixed
Close material II.
(4) double screw extruder engine speed 50r/min, one section of temperature are adjusted：185 DEG C, two-stage nitration temperature：190 DEG C, three sections
Temperature：190 DEG C, four sections of section temperature：185 DEG C, head temperature：180℃.II Jing double screw extruder melting extrusions of compound are made
Grain, obtains halogen-free expanded flame-retardant ABS resin PP Pipe Compound.
Embodiment 3
A kind of halogen-free expanded flame-retardant ABS resin, by weight percentage including following components:
Described antioxidant is the compound of irgasfos 168 and antioxidant 1076, and its mass ratio is 1:1.
The preparation method of above-mentioned halogen-free expanded flame-retardant ABS resin is with embodiment 2.
Embodiment 4
A kind of halogen-free expanded flame-retardant ABS resin, by weight percentage including following components:
Described antioxidant is the compound of irgasfos 168 and antioxidant 1076, and its mass ratio is 1:1.
Laboratory makes the synthetic route of PETA by oneself
By 5.4g (0.05mol) CaCl2, four mouthfuls of burnings of N,N-dimethylacetamide (DMAc) the addition 250ml of 180ml
In bottle, the stirring at 45 DEG C is completely dissolved calcium chloride.The ethylenediamine of 5.5ml (0.0815mol) is added afterwards.Fully dissolve
Afterwards, system temperature is down to into 0-5 DEG C with ice-water bath.The paraphthaloyl chloride of 16.24g (0.08mol) is slowly added to while stirring
(general 45min), then react a hour.System temperature is risen to into 45-50 DEG C afterwards, 22.2ml (0.16mol) is slowly added to
Four hours of triethylamine react.Reactant mixture is cooled to into room temperature, is added water and is filtrated to get white solid, wash baking with water
It is dry.
The infrared spectrum of PETA is shown in Fig. 3, and its spectrum is in 3301.7cm-1Characteristic peak of the peak at place for N-H stretching vibrations,
1633.4cm-1Locate as amidocarbonylation characteristic absorption peak, 1548.5cm-1And 1499.2cm-1Locate the characteristic absorption peak for phenyl ring,
3074.3cm-1Locate for C-H stretching vibration absworption peaks on phenyl ring, to show to have synthesized target product.
The preparation method of above-mentioned halogen-free expanded flame-retardant ABS resin is with embodiment 2.
Embodiment 5
A kind of halogen-free expanded flame-retardant ABS resin, by weight percentage including following components:
Described antioxidant is the compound of irgasfos 168 and antioxidant 1076, and its mass ratio is 1:1.
The method of laboratory self-control PETA is with embodiment 4.
The preparation method of above-mentioned halogen-free expanded flame-retardant ABS resin is with embodiment 2.
Embodiment 6
A kind of halogen-free expanded flame-retardant ABS resin, by weight percentage including following components:
Described antioxidant is the compound of irgasfos 168 and antioxidant 1076, and its mass ratio is 1:1.
The method of laboratory self-control PETA is with embodiment 4.
The preparation method of above-mentioned halogen-free expanded flame-retardant ABS resin is with embodiment 2.
Performance test is carried out to the fire proofing obtained by above example, and concrete outcome is shown in Table 1, and wherein mechanical property is surveyed
Test-object is accurate and oxygen index (OI) test is all GB.
Table 1
| Performance indications | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Impact strength (kJ/m2) | 9.64 | 4.43 | 7.44 | 8.93 | 12.39 |
| Bending strength (fM) | 63.29 | 47.68 | 62.12 | 63.77 | 57.62 |
| Tensile strength (Mpa) | 39.21 | 29.45 | 44.48 | 43.64 | 43.25 |
| Oxygen index (OI) (%) | 22.5 | 23.2 | 23.8 | 24.4 | 25.6 |
| Heat decomposition temperature (DEG C) | 275.5 | 259.4 | 289.0 | 285.8 | 287.7 |
By above example as can be seen that halogen-free expanded flame-retardant ABS resin obtained by the present invention, with good resistance
Combustion performance and mechanical property.
It is important to point out that the above, only embodiments of the invention not make any form to the present invention
On restriction；The those of ordinary skill of all industry can swimmingly be implemented the present invention by the above；But, it is all to be familiar with sheet
Technical professional is made using disclosed above technology contents in the range of without departing from technical solution of the present invention
A little change, modification and the equivalent variations for developing, are the Equivalent embodiments of the present invention；Meanwhile, all essence according to the present invention
The change of any equivalent variations that technology is made to above example, modification and differentiation etc., still fall within the technical side of the present invention
Within the protection domain of case.
Claims (8)
1. a kind of new phosphorus flame retardant, entitled 2- carboxyethyl phenyl phosphinic acids melamine salt, synthetic route is：
2. new phosphorus flame retardant according to claim 1, it is characterised in that：Preparation method is：By 2- ethoxy phenyl
Hypophosphorous acid and tripolycyanamide in molar ratio 1：1 mixing, water is solvent, 70～90 DEG C of controlling reaction temperature, reacts 3～5h, product
It is 2- carboxyethyl phenyl phosphinic acid melamine salts to obtain white solid powder after washing, drying.
3. a kind of halogen-free expanded flame-retardant ABS resin comprising phosphorus flame retardant in claim 1, it is characterised in that：Its component and
Weight percentage is：
4. halogen-free expanded flame-retardant ABS resin according to claim 3, it is characterised in that：Described ABS resin is acrylonitrile
One butadiene, one styrene copolymer, is molded rank, and proportion is 1.05g/cm3。
5. halogen-free expanded flame-retardant ABS resin according to claim 3, it is characterised in that：Described auxiliary flame retardant is Buddhist nun
Dragon 66, poly- p-phenylene ethene diamine, organic modification montmonrillonite, rare-earth oxide, polyphosphoric acid amine, melamine cyanurate
The mixture of one or more of salt.
6. halogen-free expanded flame-retardant ABS resin according to claim 3, it is characterised in that：Described antioxidant is antioxygen
Agent 168 and the compound of antioxidant 1076, its mass ratio are 1:1.
7. halogen-free expanded flame-retardant ABS resin according to claim 3, it is characterised in that：Described processing aid is white ore deposit
Oil.
8. a kind of preparation side of the halogen-free expanded flame-retardant ABS resin according to any one of claim 3 to 7 claim
Method, it is characterised in that：The method is comprised the following steps:
(1) each component is weighed according to each component percentage by weight, and dry 4 hours in 80 DEG C of convection oven；
(2) by phosphorus flame retardant, auxiliary flame retardant, in high speed material machine, mix homogeneously obtains compound I；
(3) compound I, ABS resin, antioxidant, processing aid input high speed mixer are mixed again, obtains compound II；
(4) double screw extruder engine speed 50r/min, one section of temperature are adjusted：185 DEG C, two-stage nitration temperature：190 DEG C, three sections it is warm
Degree：190 DEG C, four sections of section temperature：185 DEG C, head temperature：180 DEG C, II Jing double screw extruder melting extrusions of compound are made
Grain, obtains halogen-free expanded flame-retardant ABS resin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610846352.8A CN106519295A (en) | 2016-09-26 | 2016-09-26 | Novel phosphorus-based flame retardant and halogen-free intumescent anti-flaming ABS (Acrylonitrile Butadiene Styrene) resin containing same |
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| CN201610846352.8A CN106519295A (en) | 2016-09-26 | 2016-09-26 | Novel phosphorus-based flame retardant and halogen-free intumescent anti-flaming ABS (Acrylonitrile Butadiene Styrene) resin containing same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192339A (en) * | 2017-12-27 | 2018-06-22 | 重庆普利特新材料有限公司 | A kind of high oxygen index (OI) flame-retardant long glass fiber enhancing nylon/MMT composite materials and its manufacturing method |
| CN108623985A (en) * | 2018-04-11 | 2018-10-09 | 厦门稀土材料研究所 | A kind of rare earth cooperative flame retardant ABS material |
| CN111234537A (en) * | 2020-02-24 | 2020-06-05 | 哈尔滨理工大学 | Graphene anti-dripping flame-retardant synergist and preparation method thereof |
| CN114805936A (en) * | 2021-01-19 | 2022-07-29 | 中国石油天然气股份有限公司 | Flame retardant suitable for ABS resin, preparation method thereof and flame-retardant ABS resin |
| CN115304636A (en) * | 2022-08-15 | 2022-11-08 | 铨盛聚碳科技股份有限公司 | Organic silicon flame retardant containing phosphorus and nitrogen, and preparation method and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192339A (en) * | 2017-12-27 | 2018-06-22 | 重庆普利特新材料有限公司 | A kind of high oxygen index (OI) flame-retardant long glass fiber enhancing nylon/MMT composite materials and its manufacturing method |
| CN108623985A (en) * | 2018-04-11 | 2018-10-09 | 厦门稀土材料研究所 | A kind of rare earth cooperative flame retardant ABS material |
| CN108623985B (en) * | 2018-04-11 | 2020-08-21 | 厦门稀土材料研究所 | Rare earth synergistic flame-retardant ABS material |
| CN111234537A (en) * | 2020-02-24 | 2020-06-05 | 哈尔滨理工大学 | Graphene anti-dripping flame-retardant synergist and preparation method thereof |
| CN111234537B (en) * | 2020-02-24 | 2021-09-24 | 哈尔滨理工大学 | Graphene anti-dripping flame-retardant synergist and preparation method thereof |
| CN114805936A (en) * | 2021-01-19 | 2022-07-29 | 中国石油天然气股份有限公司 | Flame retardant suitable for ABS resin, preparation method thereof and flame-retardant ABS resin |
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