抗氧剂:塑料里的“保鲜剂”,0.1%的添加量守住一吨料的寿命

塑料知识科普 发布时间: 2026-09-14 3450 阅读

The warehouse in July was like a steamer. A batch of PP dashboard material shipped to the auto parts factory began to powder on the surface after being stored in the open yard for three weeks, flaking off as white powder with a scratch of a fingernail. The client returned the entire batch, and the logistics costs plus the restocking costs resulted in a loss of nearly 100,000 yuan. When the formulator reviewed the case, he found that only the single antioxidant 1010 was added, without the auxiliary antioxidant 168, which was completely consumed in advance under high-temperature storage.

Those few tenths of a kilogram of antioxidant in a ton of plastic are usually forgotten, but when yellowing occurs, everyone in the workshop looks for it first.

This article is compiled by Ningbo Kolong New Materials Co., Ltd., which has long been engaged in the business of plastic raw materials and additives. The grade and batch information are subject to the actual supply channels.

Quick Reference Table of Antioxidants: Four Major Systems at a Glance

Those who work with modified plastics know that antioxidants are not a single substance, but a system. The primary antioxidant is responsible for 'catching' free radicals, while the secondary antioxidant is responsible for 'breaking down' peroxides. Only the combination of the two can form a complete defense. The table below clearly lists the key parameters and typical applications of mainstream types, and when selecting a grade, first determine the system before discussing the specific product.

systemRepresentative varietiesKey parametersTypical productsAdd ratio
Blocked phenols (primary antioxidants)1010, 1076, 1098Molecular weight 500-1200, nitrogen content 0-3%Auto parts, home appliances, pipes0.1%-0.3%
Phosphite esters (secondary antioxidants)168, 626Phosphorus content 4%-10%, hydrolytic stability variesExtrusion granulation, film, fiber0.1%-0.2%
Thioester compounds (antioxidant auxiliaries)DLTDP, DSTDPSulfur content about 20%, long-lasting heat resistanceCables, hot water pipes, thick-walled parts0.1%-0.3%
Compound/Blended Type1010 168, 1076 168Main to support ratio 1:1 or 1:2General Modification of PP/PE/ABSTotal 0.2%-0.4%

Note: The parameters in the table are general ranges; differences exist among different manufacturers and grades. The actual selection should be based on the official TDS and batch test reports. The selection logic is very simple: first determine the substrate and working conditions, then choose the main antioxidant system, and finally match the auxiliary antioxidants. Do not do it the other way around.

Figure 1 Antioxidants — Oxidation Protection Barrier for Plastic Materials

Antioxidants are not better the more you add; a blend is more reliable than a single agent.

Don't rush to check the product numbers; first, get to know this behind-the-scenes player. Ningbo Cologne New Materials Co., Ltd. has long been engaged in operating various plastic additives and modified raw materials, covering sources from multiple domestic and international brands. It has stable supply channels for common additive categories such as antioxidants, light stabilizers, and lubricants. As for antioxidants, this category is essentially the 'preservative' for plastic materials—during processing and use, plastics are exposed to heat, oxygen, and light, which triggers free radical chain reactions, leading to molecular chain breakage, cross-linking, discoloration, and performance degradation. The role of antioxidants is to interrupt this chain reaction and slow down the aging process.

Antioxidants are like the 'vitamin E' of plastics; the amount is small, but without it, the material ages quickly.

Mechanistically, antioxidants are divided into two major camps. Primary antioxidants (hindered phenols, amines) capture peroxy radicals by donating hydrogen atoms, turning reactive free radicals into stable molecules; secondary antioxidants (phosphite esters, thioesters) are responsible for decomposing hydroperoxides, converting them into harmless alcohols and ketones. Their relationship is like that between fire extinguishers and firefighters in a fire brigade—one controls the fire, the other clears the area, and neither can be missing.

Primary antioxidants and secondary antioxidants are not interchangeable substitutes; they are not fighting the same battle at all.

Many newly entry formulators have a misconception: they think the more antioxidants are added, the better. In fact, excessive hindered phenol antioxidants can cause 'phenol yellowing' — in an NOx gas environment, phenolic antioxidants react to form yellow quinone structures, causing the product surface to yellow. Excessive phosphite antioxidants may hydrolyze, producing acidic substances that corrode molds and screws. So there's a saying in the industry: antioxidants are like 'MSG'; just enough to enhance the flavor is fine, adding too much can ruin the whole pot.

Oh, you call this 'aging resistance'? It became brittle and cracked after 72 hours of heat aging at 150°C, this is like taking a summer vacation.

Quick check by variety: 1010 is universal king, 1076 handles transparency, 1098 protects PA

There seem to be many grades of antioxidants, but actually focusing on a few main varieties can cover 80% of applications. Below, we break them down one by one, explaining each variety's positioning, parameters, applicable signals, and precautions.

PP-modified antioxidant formula, instead of worrying about a single agent, it’s better to mix the old duo 1010 and 168 together at once.

1010 (pentaerythritol ester of [β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]): The 'universal king' of hindered phenolic primary antioxidants, with a molecular weight of 1178, low volatility, extraction resistance, and good compatibility with resins. It can be used in almost all polyolefins (PP, PE) and engineering plastics (ABS, PBT, PS). Signals to choose it: the product is not complex, requires long-term heat resistance, and is cost-sensitive. Note: 1010 may have a risk of blooming in films and fibers; for ultra-thin products, it is recommended to switch to 1076.

Supply tip: General antioxidants like 1010 are regularly stocked by Cologne New Materials. Each batch comes with thermal aging test data. Samples can be taken by the kilogram for initial parallel comparison before deciding on bulk orders.

1076 (β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecanol ester): a hindered phenolic primary antioxidant with a molecular weight of 531, about half that of 1010, offering better compatibility with resins and less tendency to bloom. It is particularly suitable for films, fibers, and transparent products. Signals for choosing it: for making PE films, PP fibers, transparent PS/ABS parts. Note: 1076 has a lower molecular weight and higher volatility than 1010, so for high-temperature processing (>260°C), it is recommended to use in combination with 1010.

1098 (N,N’-Bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine): a hindered phenolic primary antioxidant with a molecular weight of 637, nitrogen-containing structure, specifically designed for polyamides (PA6, PA66). PA has a high processing temperature (260-290°C) and is prone to aging in hot water; 1098 has much better extraction resistance and hot water resistance than 1010. Signals for choosing it: for PA6/PA66 modification, hot water pipes, automotive engine peripheral parts. Note: 1098 is more expensive than 1010 and generally not used in non-PA substrates.

For transparent parts, choose 1076 168; for PA66 heat-resistant water applications, choose 1098 168; for high-temperature PPS/PEEK, choose 1010 626. Don't get them confused.

168 (tris(2,4-di-tert-butylphenyl) phosphite): The 'standard' secondary antioxidant among phosphite stabilizers, with a molecular weight of 647 and a phosphorus content of about 4.8%. It has good processing stability and can effectively inhibit yellowing and changes in melt flow rate during processing. It is present in almost all modified formulations. Signals to choose it: extrusion granulation, injection molding, need to suppress processing yellowing. Note: 168 is somewhat sensitive to hydrolysis, so storage in high humidity environments requires sealing, and long-term storage may lead to caking.

626 (Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite): a phosphite-type secondary antioxidant, molecular weight 604, phosphorus content about 10.3%, more than twice that of 168, with better high-temperature stability. It is especially suitable for high-temperature engineering plastics such as PPS and PEEK (processing temperature above 300°C). Indications for choosing it: modifying PPS/PEEK, high-temperature nylon, or requiring processing stability above 300°C. Note: 626 is more sensitive to hydrolysis than 168, so humidity must be strictly controlled during storage and use.

DLTDP (Dialkyl Thiodipropionate): A thioester auxiliary antioxidant with a molecular weight of 514 and sulfur content of about 12.3%. It has long-lasting heat resistance and works synergistically with hindered phenolic primary antioxidants. It is especially suitable for cables, hot water pipes, and thick-walled products that require long-term heat resistance. Choosing this indicates: making PVC cable materials, PE hot water pipes, or requiring long-term thermal stability above 100°C. Note: Thioesters have a slight odor, so caution is needed for food contact and low VOC applications.

Alternative comparison: Can imported brands be switched? Take a look at this table first

One of the most frequently asked questions by many buyers is: Can imported antioxidants be replaced with domestic ones? The answer is: Yes, but with certain conditions. The core indicators of antioxidants (molecular weight, purity, ash content, and volatile matter) show very little difference between domestic and imported products, but there are still differences in batch stability, oligomer control, and the content of colored impurities. The table below lists common replacement options and the prerequisites for switching.

Original imported directionTypical applicationsBenchmark solutionSwitch premise
BASF Irganox 1010General-purpose modification for PP/PEDomestic 1010 (multiple manufacturers)Preliminary test comparing thermal aging at 150°C × 168h, yellowing index, and MFR changes
BASF Irganox 1076Film/Fiber/Transparent PartsDomestic 1076Contrast compatibility, frosting test, transmittance change
BASF Irganox 1098PA6/PA66 hot water resistantDomestic 1098Comparison of water resistance extractives and 130°C boiling 1000h performance retention rate
BASF Irgafos 168General processing stabilityDomestic 168Comparison of hydrolytic stability, processing yellowing ΔE, and phosphorus content
BASF Irgafos 626PPS/PEEK High TemperatureDomestic 626Comparison of processing stability at 320℃, high-temperature yellowing, and hydrolytic stability

The above table is just a reference for alternative directions and does not mean that the performances of the two companies are equivalent. The correct sequence for substitution is: small-scale trial → parallel testing → written confirmation from the customer → small batch → mass production, and if there is a problem at any step, work must stop and an investigation should be conducted.

The most tedious part of substitute testing is data comparison—when Kolon New Material provides kilogram-level antioxidant samples, they include batch heat aging test data, so customers can directly run a 150℃ × 168h parallel comparison without having to build a baseline from scratch.

It still yellows even after adding antioxidants? First check the drying temperature and screw speed, don’t just blame the additives right away.

Industry Scenario Quick Reference: How the Requirements for Antioxidants Differ Among Various Products

Even though they are both antioxidants, the requirements are completely different for making car bumpers and food packaging boxes. The table below breaks it down by industry to help you quickly identify which system to use.

IndustryTypical productsThe parameters the customer asked about firstRecommendation systemCertification requirements
CarBumper, dashboard, door panelThermal aging at 150℃ × 1000h, low-temperature shock1010 168 Thioester CompoundIATF 16949, low VOC
Home appliancesWashing machine drum, air conditioner casing, refrigerator linerLong-term heat resistance, weather resistance, yellowing resistance1010 168 General CompoundRoHS, REACH
Pipe materialPPR hot water pipes, PE water supply pipes110℃ static hydraulic pressure, water-resistant extraction1010 168 DLTDPGB/T 18742, FDA
FilmBOPP packaging film, PE agricultural filmProcessing stability, light transmittance, frosting1076 168FDA, GB 4806
Electronics and electrical appliancesConnectors, coil bobbins, switchesHigh-temperature processing stability and flame-retardant synergy1010 626 (High Temperature)UL Yellow Card, RoHS
FiberPP non-woven fabric, PA industrial yarnSpinning stability and extract resistance1076 168OEKO-TEX

For a specific scenario: when making automotive dashboards, the customer requires that after thermal aging at 150°C for 1000 hours, the impact strength retention rate be greater than 80%, while also having low VOC. At this point, using only 1010 168 is not enough; thioester (DLTDP) needs to be added for long-term heat resistance, while also paying attention to the VOC contribution of the antioxidant itself—1010 has low volatility, making it more suitable for low VOC requirements than small-molecule antioxidants.

Dosage and key points of combination: Remembering four formulas is enough

The amount and combination of antioxidants follow certain rules, so you don't need to start from scratch each time. The following four formulations are industry-validated general solutions that cover most scenarios.

For PP modification to be aging-resistant, use a 1010 and 168 blend, don’t get hung up on a single agent.

◆ General PP/PE modification: 1010 (0.1%-0.2%) 168 (0.1%-0.2%), main to auxiliary ratio 1:1 or 1:2, total 0.2%-0.4%. This is the most commonly used formula, used in 80% of modified materials.

◆ Transparent film/fiber: 1076 (0.1%-0.2%) 168 (0.1%-0.2%), total 0.2%-0.4%. 1076 has good compatibility, does not bloom, and is suitable for ultra-thin and transparent products.

◆ PA6/PA66 heat-resistant water: 1098 (0.2%-0.3%) 168 (0.1%-0.2%), total 0.3%-0.5%. 1098 water resistance extraction, PA must be dried before processing (80-100℃ × 4-8h).

◆ High-temperature PPS/PEEK: 1010 (0.1%-0.2%) 626 (0.1%-0.2%), total 0.2%-0.4%. 626 has high phosphorus content and good high-temperature stability, suitable for processing above 300℃.

There are three more key points for formulation: First, antioxidants and light stabilizers have a synergistic effect. For outdoor parts, it is recommended to use HALS UV absorbers with antioxidants for a triple synergy; Second, antioxidants and flame retardants may conflict — brominated flame retardants can release HBr at high temperatures, which may consume antioxidants, so the amount of antioxidants should be appropriately increased; Third, some antioxidants in recycled materials have already been consumed. When the proportion of recycled material exceeds 30%, antioxidants should be added, usually 30%-50% of the original formula.

Don't underestimate this 0.1% antioxidant; it is quietly blocking yellowing for you in the extruder.

Antioxidant: Stability comes from blending.

Processing and Compliance Red Lines: Avoid These Four Pitfalls

If antioxidants are not used properly, the result is either yellowing or brittleness. The table below lists the key parameters of the processing steps and the consequences of mistakes; following it can help avoid eighty percent of the pitfalls.

link; segment; partReference valueThe consequences of doing wrong
Antioxidant premixHigh-speed mixer 3-5 minutes, speed 500-1000 rpmUneven mixing → local yellowing, performance fluctuations
Extrusion temperaturePP 190-230℃, PA 260-290℃, PPS 290-320℃Excessive temperature → antioxidant consumed prematurely, product yellowing
Screw speed300-500 rpm (adjust according to the machine model)Excessive rotational speed → high shear heat, accelerated consumption of antioxidants
Material DryingPA 80-100℃ × 4-8h, PC 120℃ × 3-4hNot dried → hydrolysis, antioxidant failure, product foaming
Storage conditionsCool and dry, sealed, temperature <30°C, humidity <60%Moisture absorption → Phosphite hydrolysis, caking, decreased effectiveness

Compliance red lines must also be noted: antioxidants used in food contact materials must comply with GB 4806.10 or the relevant provisions of FDA 21 CFR; for exports to the EU, compliance with REACH and EU 10/2011 is required; electronic and electrical products must comply with RoHS; automotive products must comply with IATF 16949 and the VOC standards of each car manufacturer. Compliance documents for antioxidants (FDA conformity declaration, REACH registration certificate, RoHS test report) must be requested with the goods and filed.

FAQ: The Six Most Common Questions Asked by Purchasing and Formulation Engineers

Q1: Can domestic antioxidants replace imported ones?

It is possible, but it depends on the scenario. For general modified applications (1010, 168 systems), the performance gap between domestic and imported products is already very small, and stable domestic brands can completely replace imported ones. However, in high-end scenarios (PA heat-resistant water 1098, high-temperature PPS 626, low-VOC automotive interiors), imported grades still have an advantage in oligomer control and batch consistency. The correct approach for replacement is: first, use kilogram-level samples for parallel testing, comparing key indicators such as heat aging, yellowing, and MFR changes; after passing the tests, move to small-scale trial use, and finally, scale up. When reference samples are needed, Cologne New Materials can prepare kilogram-level samples with heat aging data from the same batch, saving you the trouble of sourcing baseline material yourself.

Q2: Even after adding antioxidants, it still yellows. What is the reason?

First, check three common causes: one is that the processing temperature is too high or the screw speed is too fast, causing the antioxidants to be consumed during extrusion; two is that the material has not been dried, and moisture leads to hydrolysis, making phosphite antioxidants fail; three is that the antioxidant system was chosen incorrectly, for example using 1010 for transparent parts (which may cause frosting), or using 1010 for PA instead of 1098 (insufficient water extraction resistance). If all three are ruled out, then consider the quality of the antioxidants themselves.

Q3: Can antioxidants and light stabilizers be used together?

Not only can they be used together, but they should be. The aging of outdoor products involves both thermal-oxidative and photo-oxidative aging occurring simultaneously. Antioxidants are responsible for thermal oxidation, while light stabilizers (HALS UV absorbers) are responsible for photo-oxidation, and there is a synergistic effect between them. A typical PP outdoor component formulation: HALS 944 (0.2%), UV 531 (0.1%), 1010 (0.1%), 168 (0.1%), totaling around 0.5%. Note: HALS is alkaline and may conflict with acidic flame retardants (such as red phosphorus), so the formulation needs to be adjusted.

Q4: Is it necessary to add antioxidants to recycled material?

Necessary. Recycled materials have gone through one or more thermal processing cycles, and the original antioxidants have been consumed by 30%-70%. When the proportion of recycled material exceeds 30%, it is recommended to add 30%-50% of the original formula's antioxidant amount. For example, if the original formula contains 0.15% each of 1010 and 168, when the recycled material proportion is 50%, increase to 0.2%-0.25% each of 1010 and 168. At the same time, attention should be paid to impurities and contaminants in the recycled material, which may accelerate aging, so appropriately increasing the amount of antioxidants is a prudent approach.

Q5: What is the approximate price of antioxidants? How do you choose one with a high cost-performance ratio?

Price range of commonly used antioxidants (CNY/kg): 1010 about 30-60, 1076 about 35-65, 1098 about 80-150, 168 about 30-55, 626 about 60-100, DLTDP about 25-45. Prices fluctuate with raw material (phenol, isobutylene, phosphorus trichloride, etc.) market conditions. The principle for selecting cost-effective options is: for general scenarios, choose mainstream domestic brands; for high-end scenarios (automotive, medical, electronics), choose imported or leading domestic brands. Do not choose unknown small manufacturers just to save a few yuan—the cost of antioxidants is less than 1% of the ton cost, but the losses from problems are hundreds of times that amount.

Q6: Do antioxidants have a shelf life? Will they lose effectiveness if stored for a long time?

Yes. The shelf life of unopened antioxidants is usually 2-3 years. Storage conditions should be cool, dry, sealed, with temperatures below 30°C and humidity below 60%. Phosphite esters (168, 626) are sensitive to moisture; if not properly sealed after opening, they may hydrolyze and clump within 3-6 months, causing a significant drop in effectiveness. Hindered phenols (1010, 1076) are relatively stable, but long-term storage may also lead to oxidation and discoloration. It is recommended to use on a first-in, first-out basis and not to stockpile for more than 6 months.

Three-step checklist for choosing: Follow it to avoid pitfalls

◆ Step 1·Determine Working Conditions: First, clarify the product's usage environment (temperature, humidity, light exposure, contact media) and service life requirements, then determine which type of antioxidant system is needed (general/transparent/hot water resistant/high temperature).

◆ Step 2 · Match Parameters: According to the substrate and processing technology, refer to the quick reference table to select the combination of primary antioxidant and secondary antioxidant, and determine the addition amount (total 0.2%-0.5%, up to 0.8% in special cases). At the same time, check compatibility with other additives (flame retardants, light stabilizers, fillers).

◆ Step 3 · Certification Verification: Based on the final use of the product and the export destination, confirm the certifications the antioxidant needs to comply with (FDA, GB 4806, RoHS, REACH, UL Yellow Card, etc.), request compliance documents from the supplier, and file them.

The thermal aging data speaks for itself; only when the batch is stable do we dare to increase the volume.

The core of selecting antioxidants is not comparing unit prices, but comparing batch stability and thermal aging data. When supplying antioxidants, Kolon New Materials attaches a batch report with each shipment, and key indicators (molecular weight, ash content, volatile matter) can be traced for each batch; for customers who need to replace imports, kilogram-scale trial packs and corresponding batch thermal aging comparison data can be provided, with parallel tests conducted at 150°C for 168 hours before discussing mass supply.

That was last summer. A factory in East China that produces modified automotive PP materials was struggling under cost pressure. The previously used imported top-brand 1010 168 had a significant portion of its tonnage cost coming from additives. Kolong New Materials sent them a 1-kilogram sample of a domestic top-brand, along with batch testing data. The client's formulators conducted parallel heat aging tests in the lab at 150°C × 1000h, and the impact strength retention rate differed by only about 3% compared to the imported material. They also ran a three-month small-batch validation, and finally successfully switched, reducing the ton cost by about 40 yuan. Later, the purchasing manager said that had they known the domestic data was so stable, they wouldn’t have hesitated for more than half a year.

Check the formulation sheet—did it say 168 next to 1010?

Disclaimer: The brands, trademarks, and product names mentioned in this article are the property of their respective manufacturers. This article is a third-party material selection knowledge share. The grades, parameters, prices, certifications, and application cases mentioned are for reference only; please rely on the official latest data and batch testing reports from each manufacturer. This article does not constitute any purchasing or investment advice, and readers act at their own risk.

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