阻燃剂:塑料的“防火墙”,溴系磷系氮系无卤协效,8%到30%的添加量守住安全底线

塑料知识科普 发布时间: 2026-09-12 1150 阅读

A batch of electronic casings was sent to UL lab for testing, but after de-ignition, it continued to burn, but did not receive V-0 rating. The North American customer's order was immediately rejected. The R&D director sat in the lab all night—bromin-based flame retardant was added, but antimony trioxide synergist only added 2%, the ratio was incorrect, free radical capture was insufficient, meaning only half the firewall was built.

Plastic is not flame-retardant, like lighting a candle in a paper house; on the day of acceptance, UL94 was completely exposed by a fire.

This article was compiled by Ningbo Kelong New Materials Co., Ltd., a long-term business in plastic raw materials and additives. Grade and batch information are subject to actual supply channels.

Flame Retardant Quick Reference Summary: Bromine, phosphorus, nitrogen-based, and halogen-free routes

Flame retardants are divided into four main categories by chemical route: bromine based is highly efficient maturing, phosphorus and nitrogen is halogen-free, and metal hydroxides are halogen-free but require high filling. When selecting a model, first decide the route—whether halogen-free is needed, which substrate to use, what flame retardant rating is required, and then choose the specific variety.

SystemRepresentative VarietiesFlame Retardant MechanismTypical ProductsAdded Ratio
Bromine Series + SynergisticDecabromodiphenylethane + Sb2O3Vapor Phase Free Radical CapturerElectronics and Electrical Appliances, Glass Fiber Reinforcement8%-15%
Phosphorus-basedRed phosphorus, polyammonium phosphate, aluminum hypophosphiteCoagulated zone carbon-formingPP, PA, PET flame retardant10%-20%
Nitrogen-basedMelamine and its saltsVapor dilution, carbon-formingPA, PP expansion type10%-20%
halogen-free synergyPhosphorus + nitrogen-based + aluminum hydroxide/magnesiumVapor phase + cohesive zone synergyhalogen-free cable, new energy15%-30%.
Metal HydroxidesAluminum hydroxide, magnesium hydroxideHeat absorption, dilution, carbon formationHalogen-free and low smoke, Building materials30%-60%

Note: The above flame retardant grades and additive amounts are industry references; actual flame retardant effects are subject to UL official yellow cards and third-party testing. Large amounts of flame retardants are added, making them cost-sensitive and often leading to mechanical degradation. Formulas must be tough and flame-retardant together.

Figure 1 Flame retardants — the fire barrier on plastic surfaces

Flame retardants are the firewall on plastics; when they burn, they shield you from that attack.

The protagonist is the firewall of plastics. Ningbo Kelong New Materials Co., Ltd. has long operated various plastic additives and modified raw materials, covering multiple domestic and international brands, with stable supply in bromine-based, phosphorus-based, nitrogen-based, and halogen-free synergistic flame retardant systems. Flame retardants are essentially the "firewall" of plastics. Plastic decomposes into combustible gases when exposed to fire, maintaining chain combustion. The function of flame retardants is to break this chain—either trapping free radicals in the gas phase to suppress the flame, or carbonizing the material surface to keep oxygen and heat out.

Flame retardant isn't just about adding more to get safer. When the synergistic ratio and dispersion are in place, only when it really burns can it withstand that moment.

Take brominated + antimony trioxide (Sb2O3) synergy: when decabromodiphenylethane is heated, it releases gases like hydrogen bromide. Sb2O3 reacts with it to form more efficient gas-phase flame-retardant species. The ratio of 1+1 is greater than 2—that's 'synergy.' The halogen-free route relies on phosphorus-based catalytic carbonization in the cohesive zone, nitrogen-based gas dilution in the gas-phase phase, metal hydroxides absorbing heat for cooling, and releasing water vapor—working on multiple approaches simultaneously. Each mechanism has its own focus; it's not just random stacking.

Bromine-based flame retardants release gases that trap free radicals when heated, like weaving an invisible fire net outside the flame.

A common misconception: the more flame retardants added, the higher the grade. In fact, excessive flame retardants seriously sacrifice mechanics, flow, and weather resistance, and may even precipitate; Without adding synergists, relying solely on bromine-based or phosphorus-based systems greatly reduces efficiency. The industry consensus is: blending synergy—achieving the same grade with a smaller amount is the real skill.

Oh, you mean "flame retardant"? If you burn as soon as you leave the flame, or burn after leaving the flame, that's called burning quite strong, not flame retardant.

Quick product search: bromine-based with Sb2O3, halogen-free with phosphorus, nitrogen, and hydroxide

There are many types of flame retardants; just focus on the four main lines. Next, I'll explain the positioning and precautions one by one.

Choosing a flame-retardant route is like choosing a fire lane: whether halogen-free or bromine-based must be decided before work starts, and changing direction halfway through burning is too late.

Decabromodiphenylethane + antimony trioxide: A classic bromine-based flame-retardant combination, high efficiency and relatively controllable cost, widely used in glass fiber reinforced PP/PA and electronic electrical devices. The bromide antimony ratio is commonly about 3:1. Signal for choosing it: Cost-sensitive, halide-based substrates allowed, must be stable above UL94 V-0. Note: Halogen-containing and halogen-free parts must not be used; Sb2O3 has certain usage restrictions, so please check regulations.

Supply Tip: Bromine-based, phosphorus-based, and nitrogen-based flame retardants Kelon New Materials can supply supporting supply. Each batch includes reference data for flame retardant ratings, and kilogram-level samples support UL pre-testing first.

Phosphorus-based flame retardants (red phosphorus, polyammonium phosphate, aluminum hypophosphite): The main product for halogen-free routes, relying on coagulation zone carbonization. Red phosphorus has high flame retardant efficiency but must pay attention to color and safety; Polyammonium phosphate is mostly used for expansion types; Aluminum hypophosphite is suitable for glass fiber reinforced systems such as PA and PBT. Choose its signal: halogen-free and require a high flame retardant rating. Note: Phosphorus-based products are sensitive to processing temperature and hydrolysis; PA/PB must be thoroughly dried.

Halogen-free is not just about adding a little bromine; it involves the vapor phase, condensation zone, and heat absorption all working together; any one will leak air.

Nitrogen-based flame retardants (melamine and its salts): mainly used for PA and PP, releasing non-combustible gases and expanding into carbon in the gas phase. They often form intumescent flame-retardant systems with phosphorus-based systems. Signal when selecting: halogen-free, PA/PP flame-retardant. Note: Nitrogen-based flame retardants may be separated from ammonia at high temperatures; processing and odor must be evaluated.

Metal Hydroxides (aluminum hydroxide, magnesium hydroxide): Truly halogen-free with low smoke, but low flame retardancy efficiency, requiring 30%-60% to be sufficient, significantly increasing density, sacrificing mechanics and flow. Suitable for cables and building materials with high requirements for smoke density and halogen-free. Choose its signal: halogen-free, low-smoke cables and building materials. Note: High filling, must be coupling to improve interface.

Halogen-free synergistic blending system: Mix phosphorus, nitrogen, and metal hydroxides in proportion, balancing efficiency and halogen-free, which is the direction for new energy and halogen-free cables. Choose its signal: halogen-free + higher flame retardancy + mechanically acceptable. Note: The blending system should follow the manufacturer's recommended ratio; random mixing may cause flame retardancy and substandard standards.

Adding flame retardants reduces material properties and increases costs. This is their temperament; if you are mentally prepared in advance, you won't panic.

Substitution Comparison: Switching from imported flame retardant systems to domestic ones first passes UL94

Procurement FAQ: Can imported flame retardants be replaced domestically? The answer is that the gap between general bromine and halogen-free systems has narrowed, but flame retardant rating testing and regulatory compliance are hard hurdles and must be tested. The key to flame retardants is the content of active ingredients and the synergistic ratio, which mainstream domestic brands can already match. The table below lists common substitution directions and switching prerequisites.

Original imported directionTypical applicationsBenchmarkable solutionsSwitching prerequisites
Imported brominated flame retardantsElectronics and electrical appliances, glass fiber reinforcementDomestic decabromodiphenylethane + Sb2O3Comparison of UL94 rating, mechanical properties, and precipitation
Imported red phosphorus/phosphorus-basedPA/PET Halogen-Free Flame RetardantDomestic phosphorus-based flame retardantCompare flame retardant grade, hydrolysis, color
Imported expandable nitrogen-phosphorus systemPP halogen-freeDomestic phosphorus-nitrogen synergistic effectComparison of carbonization, smoke density, and processing window
Imported halogen-free synergistic systemNew energy, halogen-free cablesDomestic phosphonitride hydroxide compoundComparison of UL94, GWIT, and mechanical retention
Imported magnesium/aluminum hydroxideLow-smoke halogen-free cableDomestic metal hydroxideComparison of oxygen index, density, and interface

The table is for application reference and does not imply complete equivalence in performance. Replacement sequence: lab scale → UL94 parallel testing → customer written confirmation → small batch → mass production.

Flame retardant substitutes must pass UL pre-testing. When Cologne New Materials sends kilogram-scale samples, they can provide flame retardant grade references and halogen compliance documents. Customers can first conduct internal burn tests before sending to a third party, saving certification time.

In order to save on flame retardant, they added 20–30% more filler, but as a result, the flame retardant level didn't meet the standard, and the whole batch was returned. This deal ended up being a complete loss.

Industry Scenario Quick Lookup: Flame Retardant Ratings Follow Safety Standards

Even though they are both flame retardants, the systems and regulations are completely different for electronic connectors and halogen-free cables. The table below breaks this down by industry.

IndustryTypical productsThe parameters the customer asked about firstRecommended planCertification requirements
Electronics and electrical appliancesConnectors, switches, coil coresUL94 rating, GWIT, CTIBromine-based Sb2O3 or halogen-free phosphorus-basedUL Yellow Card, RoHS
CarInterior, wiring harness, battery perimeterLow smoke, halogen-free, thermal agingHalogen-free phosphorus-nitrogen synergismIATF 16949, ECE R118
CableBuilding lines, control lines, photovoltaic linesOxygen index, smoke density, halogen-freeHydroxide/halogen-free synergistic effectGB/T 19666, IEC
new energyBattery pack structural components, bracketsHalogen-free, flame-retardant, low-toxicityHalogen-free phosphorus-based synergistUL94, OEM specifications
Building materialsPipes and decorative panelsFlame retardant, smoke densityHydroxide/ExpandableGB 8624
Home appliancesShell, internal componentsUL94, heat resistanceBrominated or halogen-freeUL, RoHS

Here's a specific scenario: making halogen-free brackets around new energy battery packs, requiring UL94 V-0, halogen-free, and low smoke. At this point, phosphorus-based, nitrogen-based, and a small amount of metal hydroxides are used in a compound, with an addition of about 15%-25%. At the same time, POE-type toughening agents are added to compensate for the impact reduction caused by the flame retardants, adjusting flame retardancy and rigidity-toughness together.

Dosage and matching points: synergistic blending, avoid piling ingredients at a single point

Flame retardants are the additives used in the largest amounts, and synergistic formulations can achieve the target level with even smaller additions. The following four formulations cover the mainstream routes.

Under the halogen-free trend, it's much better to become familiar with the phosphorus-nitrogen synergistic system early rather than switching formulas at the last minute.

◆ Brominated glass fiber reinforced: Decabromodiphenyl ethane 12%-14% Sb2O3 about 3%-5%, used for PP/PA electronic parts, target UL94 V-0.

◆ Halogen-free PA: Aluminum hypophosphite/phosphorus-based 10%-15%, PA should be thoroughly dried, pay attention to hydrolysis and precipitation.

◆ Halogen-free expandable PP: Phosphorus-based and nitrogen-based compounds 15%-20%, flame retardancy relies on char formation, pay attention to processing temperature window.

◆ Halogen-free low-smoke cable: 30%-60% aluminum/magnesium hydroxide, with a coupling agent to improve the interface, and with an impact modifier to enhance toughness.

Three key points for formulation: First, flame retardants are often used together with toughening agents because flame retardants reduce impact strength, which POE-type agents can compensate for; second, brominated flame retardants may consume antioxidants at high temperatures, so appropriate antioxidant supplementation is needed; third, for glass fiber reinforced parts, special attention is needed when making them flame retardant, as glass fibers can create a 'wick effect' that promotes burning, so the amount of flame retardant needs to be higher than in non-glass fiber systems.

Flame retardants fear procurement that only looks at price and ignores the UL yellow card; only when it catches fire do they remember the compliance account.

Flame retardant: compounded synergistic effect.

Processing and Compliance Red Lines: Precipitation, Hydrolysis, UL Yellow Card

If flame retardants are not used properly, they either precipitate or fail to meet the flame retardancy standards. The table below lists the key parameters and the consequences of mistakes.

link; segment; partReference valueThe consequences of doing wrong
Flame retardant dispersionHigh-speed mixing until uniform, granulate masterbatch if necessaryUneven dispersion → Local flame retardancy not up to standard
Phosphorus-containing system dryingPA/PBT 80-120℃ × 4-8hNot dried → decreased hydrolysis and flame retardant efficiency
Processing temperatureAccording to the substrate, avoid premature decomposition of the flame retardantExcessive temperature → flame retardant decomposition, odor
synergy ratioBromine:antimony about 3:1, according to the manufacturer's recommendationImbalanced ratio → low flame retardant efficiency, high cost
Compliance ArchivingUL Yellow Card, RoHS, REACH, Smoke DensityNo documents → Customer does not acknowledge, shipping stalls

Compliance Red Lines: Electronic parts must have UL94 yellow card and GWIT/CTI; exports to the EU require REACH (some brominated flame retardants such as polybrominated biphenyl ethers are restricted); automotive parts must meet the vehicle manufacturer's flame retardant and low smoke standards; halogen-free parts must comply with the corresponding halogen-free and smoke density standards. Compliance documents should be requested with the goods for filing.

FAQ: Five Common Questions Asked by Procurement and Formulation Engineers

Q1: Can domestic flame retardants replace imported materials?

It's possible, but flame retardancy is a strict test. For general brominated and conventional halogen-free systems, the gap between mainstream domestic brands and imported ones is already small, and stable domestic brands can be used as replacements. However, in scenarios like new energy halogen-free materials, high-end electronic UL yellow card, and low-smoke halogen-free materials, imported grades still have advantages in synergistic formulation and batch consistency. The correct approach is to first perform parallel UL94 testing with kilogram-level samples, comparing ratings, GWIT, and mechanical property retention, and after passing, scale up with small batches. For reference samples for testing, you can request kilogram-level samples from Cologne New Materials and compare them along with the batch data.

Q2: Why does it still fail to pass V-0 even after adding flame retardant?

Check three points first: one, no synergist was added, so the efficiency of a single agent is insufficient; two, the candlewick effect of the glass fiber amplifies burning, and the amount is insufficient; three, uneven dispersion or decomposition of the flame retardant during processing. Using a compounded synergist, adjusting the core ratio, and controlling the temperature are often more effective than simply adding more.

Q3: How to choose between brominated and halogen-free?

Look at customer requirements and regulations. If halogenated materials are allowed, cost-sensitive, and need stable V-0, brominated Sb2O3 has a high cost-performance ratio; if the customer explicitly requires halogen-free, has export restrictions, or is in the new energy sector, use phosphorus-nitrogen synergistic or metal hydroxides. Do not use brominated materials in halogen-free parts, and do not force high-filled hydroxides in cost-sensitive parts.

Q4: Will flame retardants make the material brittle?

Yes, especially in halogen-free highly filled hydroxide systems. The strategy is to use POE-type toughening agents and coupling agents to improve the interface, compensating for the lost impact, and balance rigidity, toughness, and flame retardancy together.

Q5: What is the price range of flame retardants?

Common price ranges vary greatly: brominated around 15-40 yuan/kg, phosphorus-based around 20-60, nitrogen-based around 20-50, aluminum hydroxide around 5-15, magnesium hydroxide around 10-25, fluctuating with market conditions and subject to current quotations. The amount of flame retardant added is large, making it a major part of the formulation cost; choosing the right synergistic formulation is more important than cutting the unit price.

Three-Step Selection Checklist: Follow It Without Pitfalls

◆ Step 1 · Set the route: First confirm whether it should be halogen-free, the target UL94 rating, the substrate, and whether it contains fiberglass, then decide on a bromine-based synergistic approach or a phosphorus-nitrogen/hydroxide route.

◆ Step 2 · Formulate: Determine the ratio of flame retardant to synergist according to the route (bromine:antimony about 3:1, etc.), evaluate the impact on mechanical properties and flow, and add toughening agents and coupling agents if necessary.

◆ Step 3·Pass Testing: Conduct UL94, GWIT, and smoke density parallel tests to confirm that the rating meets the standard, then verify the UL Yellow Card, RoHS, and REACH according to the intended use and file the records.

I can only sleep after I get the UL yellow card in hand and the order confirmed.

The selection of flame retardants should simultaneously consider the flame retardant level, substrate compatibility, compliance requirements, and cost. Kolon New Materials supplies brominated systems (decabromodiphenyl ethane with Sb2O3 synergist), phosphorus-based systems (BDP/RDP), nitrogen-based systems (MCA), and halogen-free synergistic systems, and can provide UL Yellow Card references as well as RoHS/REACH compliance documents. Different substrates (PP/ABS/PC/PA) can be recommended with corresponding systems, and kilogram-scale samples are supported for preliminary flame retardant testing before finalizing the formulation.

That was last year. A factory producing electronic connectors wanted to enter the North American market, but their UL94 V-0 test failed twice. Manager Wu from Cologne looked at their formula and saw that they had added 12% brominated compounds, but only 2% Sb2O3, so the synergistic ratio was incorrect. He suggested adjusting it to about 10% brominated compounds and about 4% Sb2O3, and added antioxidants to prevent degradation of the flame retardants during processing, and sent the corresponding samples. On the third test, the client passed V-0. After receiving the UL yellow card, their North American orders went through smoothly. The R&D director said that it turns out that more is not always better for flame retardancy; the proportion has to be right.

For bromine compounds and antimony trioxide, what is your ratio?

Statement: The brands, trademarks, and product names mentioned in this article are owned by their respective original manufacturers. This article is a third-party material selection knowledge sharing; the grades, parameters, prices, certifications, and application cases mentioned are for reference only. Specific information should be based on the latest official data and batch inspection reports from the respective manufacturers. This article does not constitute any procurement or investment advice, and readers bear the risks of any actions taken based on it.

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