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Green flame-retardant

Time: 2018-07-11
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Green flame-retardant

With the increasing awareness of global safety and environmental protection, people have more and more requirements on fire safety and flame retardant of products.

At present, nearly 80% of the flame retardants used for plastics modification in China are halogenated flame retardants, which are represented by polybrominated diphenyl ethers and polybrominated biphenyls. Brominated flame retardants are of high efficiency and low dosage, and have little influence on the properties of materials, and their prices are moderate.

Compared with other types of flame retardants, the performance/price ratio of these flame retardants is more superior.

But the bromine - antimony flame retardant system on the pyrolysis and combustion generates a lot of smoke and corrosive gas, and in recent years, some eu countries think bromine flame retardants on combustion would produce the toxic carcinogenic polybrominated generation of benzene and evil ying (PBDD) and polybrominated diphenyl and furan (PBDF), in February 2003, the European Union RoHS and WEEE two ban, including RoHS is limit of harmful substances (TheRestrictionofHazrdOusSubstancesDirective), its regulation since January 1, 2006,

All electronic and electrical equipment sold in eu countries shall not contain polybrominated biphenyls or polybrominated diphenyl ethers.

Environmental friendly flame retardant is often used

Environmental friendly bromine flame retardant

1. 10-brominated diphenyl ethane 80108010 does not belong to polybrominated diphenyl ether. It is absolutely impossible to produce PBDD or PBDF in combustion.

The relative molecular weight of 8010 is 971.

The bromine content was 82%, equivalent to that of DBDPO (83%), so the flame retardant performance was basically the same.

Stability were DBDPO melting point 345 ℃, at the beginning of the high (305 ℃);

Its light resistance and non-dialysis resistance are superior to DBDPO, and the most valuable is that its flame retardant plastics can be recycled, which is a characteristic that many bromine flame retardants do not have.

The product 8010 is white crystalline powder with an average particle size of 3 pleurim, free flow and micro granulation. It is easy to disperse in plastic modification, and the color of plastic products is free.

Moreover, the industrialization cost is equal to DBDPO, and it is the most ideal substitute for DBDPO.

As an additive bromide flame retardant, 8010 also needs to be used with antimony in the process of use, and the proportion of matching is the same with DBDPO/ antimony.

Compared with DBDPO, 8010 is more suitable for engineering plastics with high temperature and high viscosity.

The first company to industrialize 8010 production was American yabao corporation, and applied for the production and use patent;

However, it was found that the scope of patents of yabao company was outside China, so it could produce and use 8010 in China, but could not export or apply for patents.

By the end of 2002, it was successfully tested on an industrial scale.

2. Brominated epoxy resin

Flame retardant USES brominated epoxy resin, also known as tetrabromobisphenol A epoxy resin oligomer, the bromine content can be up to 50%, the molecular weight is between 1000 and 45,000, divided into EP type and EC type.

Compared with EC type, EP type has good light resistance, but low bromine content, while ABS and HIPS have good impact strength.

Commercial brominated epoxy resin is a mixture of cream yellow semi-transparent wafers and white powder.

Brominated epoxy resin has satisfactory melt flow rate and higher flame retardant efficiency, excellent thermal stability and light stability, and can give a good mechanical property of flame retardant base material, the product does not have frost.

Low phase molecular weight brominated epoxy resin is applicable to flame retardant ABS and HIPS. High phase molecular weight is suitable for flame retardant ABS/PC alloy and engineering plastics such as PC, PET and PBT.

It needs to be used in conjunction with antimony compounds during use.

As one of the most famous brominated epoxy resin flame retardant manufacturers in the world, Dead Sea bromine company of Israel has perfect production technology and excellent product quality.

It was once the only brand in the domestic brominated epoxy resin flame retardant market.

Since 2002, the brominated epoxy resin has been commercialized successively in shandong laiyu chemical industry, but the product quality is not satisfactory.

At present, domestic market representative products are: Israel Dead Sea bromine company F2100F2400, shandong laiyu chemical, Taiwan changchun BEB series.

3. Brominated polystyrene

The development of brominated polystyrene is similar to that of brominated epoxy resin.

The brominated polystyrene is white or light yellow powder or granule, the bromine content is about 60%.

Thermal decomposition temperature greater than 310 ℃, with large molecular weight, good thermal stability, good dispersion and mixing in the high polymer capacitive, easy processing, no cream, etc.

Brominated polystyrene is named as brominated polystyrene and polybrominated styrene according to its synthesis pathway. It can be seen from the naming that brominated polystyrene is completed by brominating polystyrene.

Polybrominated styrene is prepared by polymerization of styrene first by enbonds protection, then by bromination, and then by restoring the alkene bonds and synthesizing styrene bromide.

From the synthesis whether the use of solvent, can be divided into solvent method and non - solvent method.

Because the solvent method USES less bromine, people usually use the solvent method for synthesis.

Brominated polystyrene is mainly used in thermoplastic resins such as PA, PBT and PET.

When flame retardant polyester is added at 13% (reinforcement) ~ 17%(non-reinforcement), it can be assigned to material ul94v-o (0.8mm); when flame retardant polyamide is added at 21%, it can be assigned to material ul94v-o (0.8mm).

Great lakes and yabao are famous manufacturers of brominated polystyrene, whose products once led the domestic market. Now some domestic flame retardant manufacturers, such as shouguang Marine chemical co., LTD.

P series flame retardant

1. Red phosphorus master grains

Among the non-halogenated flame retardants, red phosphorus is a good flame retardant.

Common red phosphorus is easy to absorb moisture and has poor compatibility with polymer materials.

The microencapsulated red phosphorus flame retardant reduced the activity of red phosphorus and solved the compatibility. The content of red phosphorus was around 85%, but the problem of spontaneous combustion was not effectively solved, and the dust pollution was serious.

Red phosphorus master grains are dark red particles with red phosphorus mixed with aluminum hydroxide and expanded graphite.

It has low smoke and high flame retardant efficiency.

No dust pollution, excellent processing performance;

Low density, good thermal stability and less physical property degradation;

No frost, migration and corrosion during processing.

In particular, products with high leakage trace index (CTI), electronic appliance application has obvious advantages.

.

The main drawback of red phosphorus master grains is the color problem, except dark red and black, can not give products more color choices.

Red phosphorus master grains are used for flame retardant of general plastics, rubber, polyethylene, polypropylene and other materials lacking oxygen elements. It is best used in combination with magnesium hydroxide and aluminum hydroxide.

Flame retardant for oxygen-rich materials such as PET, PC, PBT and PA can be used alone.

In order to achieve the best dispersibility of red phosphorus, a certain amount of dispersants can be prepared.

2. ReofosRDP


It has a high p content of 10.8%.

It has the characteristics of high flame retardant, low additive amount and little effect on the properties of finished products.

It has the dual function of flame retardant and plasticizer, which can make the flame retardant fully realize halogen-free, improve the flow processing performance in plastic molding and reduce ablation, improve the thermal aging performance, improve the thermal deformation temperature, and inhibit the residue after combustion.

When used, resorcinol bisphenol (diphenyl phosphate) is generally used separately and does not need to cooperate with other flame retardants. It is mainly used for some high-functional styrene copolymer, such as PPO/HIPS and PC/ABS.

When HIPS/PPO was flame-retardant, the dosage was around 11%, the oxygen index reached 37%, and the level of UL94 (1.6mm) reached v-o and level.

When the flame retardant PC/ABS alloy is related to the proportion of both PC/ABS, the dosage is generally between 6% and 10%.

Oxygen index reached 29%, and UL94 (1.6mm) reached v-o and grade.


But there are not many mature products on the market.

The main domestic sales manufacturers for the United States lake products.

Nitrogen series flame retardant

Nitrogen series flame retardant is a compound of melamine and phosphorus, mainly including melamine, melamine cyanuric acid and melamine phosphate.

In general, nitrogenous flame retardant is white crystalline powder with 10 p ~ 50 p particle size and easy to disperse.

Density: 1.5cm ~ 1.7g/cm.

As a new type of flame retardant, nitrogen flame retardant has many advantages.

Halogen free;

There is no corrosion, thus reducing the problem of mechanical corrosion;

Resistance to ultraviolet light;

Good electrical performance, the most obvious advantage in electronic appliances;

Does not fade, does not spray frost;

It can be recycled and reused.

Nitrogen series flame retardants are mainly used in polyolefin and polyamide.

For the non-reinforced nylon, the flammable grade can reach UL94V-O at the additive amount of 8%.

For PP, the combustible level can reach UL94V-O level when the additive amount is 25%.

Excellent cost/performance ratio.

Dutch DSM product Melapur?

200 is a nitrogen flame retardant suitable for glass fiber reinforced PA66. The flammable grade reaches UL94V-O at 25% of the additive amount.

And processing temperature can be as high as 320 ℃.

The Dutch company DSMMelapur is one of the most famous nitrogen flame retardant manufacturers in the world. Its products are melapur-mc, melapur-mp and melapur-200 series.

At present, there are many factories producing MC series of nitrogenous flame retardant, and the product quality is average.

Inorganic flame retardant

Inorganic flame retardants are mainly aluminum hydroxide and magnesium hydroxide. At present, inorganic flame retardants have been widely used in foreign countries, among which the consumption of the United States, Japan and Western Europe accounts for 60%, 64% and 50% of the total consumption of flame retardants respectively.

Aluminum hydroxide and magnesium hydroxide are both white powders with a relative density of about 2.4 and a particle diameter of 1 ~ 20 nm.

Aluminum hydroxide to dehydration temperature 200 ℃, magnesium hydroxide to dehydration temperature 340 ℃.

Magnesium hydroxide, high thermal decomposition temperature is 140 ℃ higher than aluminum hydroxide, can add the synthesis of magnesium hydroxide material can withstand the higher processing temperature, extrusion speed, shorten the molding time, also helps to improve the flame retardant efficiency.

The magnesium hydroxide particle size is small and the equipment wear is small.

As magnesium hydroxide has many advantages compared with aluminum hydroxide, magnesium hydroxide accounts for an increasing proportion.

Compared with similar inorganic flame retardant, magnesium hydroxide has better smoke suppression effect.

Magnesium hydroxide does not discharge harmful substances in the process of production, use and waste, and it can neutralize the acidic and corrosive gases produced in the combustion process.

When aluminum hydroxide and magnesium hydroxide are used alone as flame retardants, the dosage is generally between 40% and 60%, which seriously affects the mechanical properties of the materials.

Uniform dispersion becomes the most important problem in machining engineering.

The surface modification of magnesium hydroxide by selecting the surface modifier with excellent performance is the first work before the use of magnesium hydroxide.

The purpose is to improve the surface activity of the particles, improve the dispersion, improve the flame retardant effect, improve the compatibility with polymer materials, and improve the impact resistance and thermal properties.


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