News Details
Soft PVC flame retardant
2017-11-10 15:34:50
Soft PVC flame retardant
Polyvinyl chloride (PVC) products can be divided into two categories: hard and soft. The chlorine content of PVC reaches 56%, and its oxygen index is greater than 45. Therefore, hard PVC only needs further flame retardant in extreme cases.
The addition of 65 soft PVC flame retardants (100 phr PVC) in soft PVC to flammable ester plasticizers (such as phthalic acid, two formic acid, two octyl ester), the chlorine content can be reduced to 36%, and the oxygen index can be as low as 22. At the same time, soft PVC because of small hardness, can replace rubber in a certain occasion, so widely used in buildings, automobiles, cables and other flame retardant requirements of the industry, so soft PVC flame retardant is necessary. At present, there are many soft PVC flame retardants, including phosphate ester, chlorinated paraffin, three oxidation of two antimony, magnesium hydroxide (MDH), zinc borate, etc..
PPFBS is a soft PVC flame retardant for polycarbonate. The addition of 0.06%--0.1% PPFBS in polycarbonate can make the flame retardancy of the material reach UL-94V-0 (3.2mm thickness). It should be noted that the dosage of more than 0.1%, not only can not improve the flame retardant properties of the material, but also affect the transparency of polycarbonate.
In order to meet the higher flame retardant requirements, a small amount of siloxane can be used to make the compound. When the amount of siloxane is 0.02%--0.3% of the total amount of the formula, the flame retardancy of 1.6mm thick sample can reach UL-94V-0 grade. The most common use is poly (methyl phenyl siloxane), but some of the siloxane effects on the transparency of polycarbonate by PPFBS.
Studies have shown that viscosity is minus 6 square 1 x 10 to 3 x 10 4 negative m2 / S (20 C) of polymethylphenylsiloxane has a synergistic effect to the PPFBS, and the viscosity is 4 x 10 minus 6 square to 2 x 10 5 negative m2 / S (20 C), polymer molecular chain has more than two silicon atoms.
The price of PPFBS is higher, and PPFBS is replaced by partial KSS in practical application to reduce cost. For example, adding 0.02% PPFBS and 0.3% KSS in polycarbonate can make the material reach UL-94 V - 0 (1.6mm thick)
In the sulfonate soft PVC flame retardant used in polycarbonate: KSS is widely used, it does not contain halogen, environmental protection economy. Adding 0.05%--0.1% can increase the oxygen index of polycarbonate from 27% to 37%, and it will not affect the transparency of polycarbonate.
The deficiency is used alone can not meet the requirements of flame retardant high, such as thin-walled parts (not less than 2.5mm thickness) of the flame retardant level UL-94V-0. In practical application, it is often used in combination with polysiloxane. In addition, if a small amount of fluoropolymer is added at the same time, the flame retardancy of the material will be better. Among them, PAPSQ is poly (propyl / phenyl) silsesquioxane, and PVDF is polyvinylidene fluoride.
Tris(2-chloroethyl)phosphate(TCEP)
There Are Three Industrial Methods: Phosphorus Oxychloride And Chloroethanol Reaction; Phosphorus Trichloride And Chloroethanol Reaction Reoxidation; Phosphorus Oxychloride And Ethylene Oxide Reaction (Industrial Commonly Used Method).
1, Phosphorus Oxychloride And Ethylene Oxide To Sodium Metavanadate As A Catalyst, At 50 ° C Reaction, The Reaction By Neutralization, Washing, Vacuum Dehydration Off The Low Boiling, That Is, The Finished Product. Chlorohydrin Can Also Be Used As Raw Materials, And Phosphorus Oxychloride Or Phosphorus Trichloride Reaction To Produce Tris (2-Chloro Ethyl) Phosphate.
2, 326 Kg Of Phosphorus Oxychloride And 1.0 Kg Of Sodium Metavanadate Into The Reactor. The Nitrogen In The Autoclave Was Driven By Nitrogen, And 650 Kg Of Ethylene Oxide Was Introduced Under Vacuum And Stirred At 45 To 50 ° C For 2 To 3 Hours. Evaporation Of Excess Ethylene Oxide After Alkali Neutralization To Neutral, Washed, Vacuum Dehydrated. Finished Product.
3. Put Phosphorus Oxychloride And Sodium Metaphosphate Into The Reactor. Nitrogen To Drive The Air, In The Vacuum Under The Access To Ethylene Oxide, At 45 ~ 50 ℃ Stirring 2 ~ 3h. Evaporation Of Excess Ethylene Oxide After Alkali Neutralization To Neutral, Washed, Vacuum Dehydrated Finished.
Tris(2-chloroethyl)phosphate(TCEP)Use:
1. Tris (2-Chloroethyl) Phosphate Has Excellent Flame Retardancy, Excellent Resistance To Low Temperature And UV Resistance, The Steam Can Only Be Used At 225 ℃ Above The Direct Ignition Can Be Fired, But The Fire The Source Is Immediately Self-Extinguishing. This Product Is A Flame Retardant Not Only Can Improve The Material Level Of Flame Retardant Materials, But Also Improve The Flame Resistance Of Water Resistance, Acid Resistance, Cold Resistance And Antistatic Properties. Commonly Used In Flame Retardant Nitrocellulose And Acetate Fiber As The Substrate Of Paint Coatings, Unsaturated Polyester, Polyurethane, Acrylic, Phenolic Resin, Can Also Be Used For Soft PVC Plastic Flame Retardant. This Product Is Used For The Amount Of Unsaturated Polyester 10% To 20%, In The Polyurethane Rigid Foam (Flame Retardant Polyether As Raw Material) Can Be About 10% In The Soft PVC Used As Auxiliary Plastic Flame Retardant When The 5% To 10%. Flame Retardants, Uranium, Thorium, Plutonium, Technetium And Other Rare Metal Separation Solvent Or Extractant.
2. This Product Is Widely Used In Chemical Fiber Fabrics, Cellulose Acetate As A Flame Retardant, In Addition To Self-Extinguishing, But Also Improve Water Resistance, Cold Resistance And Antistatic Properties. The General Amount Of 5 To 10 Copies. This Product Is An Excellent Flame Retardant For Synthetic Materials, And Has A Good Role In The Promotion, Widely Used In Cellulose Acetate, Nitrocellulose Varnish, Ethyl Cellulose, Polyvinyl Chloride, Polyvinyl Acetate, Polyurethane, Phenolic Resin , In Addition To Self-Extinguishing Products, But Also Improve The Physical Properties Of Products, Products Feel Soft, Also Known As Oil Additives And Rare Elements Of The Extractant, And Flame Retardant Rubber Conveyor Belt Is The Main Flame Retardant Materials , The General Amount Of Added 5% To 10%.
3. Used As Additive Type Halogenated Phosphate Flame Retardant And Plasticizer. Molecules In Both Phosphorus And Chlorine, Flame Retardant Effect Is Remarkable, Not Volatile And Hydrolysis, Good Stability To Ultraviolet Light. Applicable To Phenolic Resin, Polyvinyl Chloride, Polyvinyl Acetate, Polyurethane And So On. Also Used As Nitrocellulose Coating Flame Retardant, PVC Flame Retardant Plasticizer, Metal Extractant, Gasoline Additives And Polyimide Processing Aids And So On. Can Improve Water Resistance, Weatherability, Cold Resistance, Antistatic Property. Reference Dosage 5% To 20%.
From Figure 2 a curve can be seen a small amount of KSS can be made of polycarbonate oxygen index increased significantly when adding 0.1% reaches a maximum value of 38.3%, then decreased; D line KSS and PAPSQ, PVDF display, flame retardant polycarbonate oxygen index is greatly improved, when the dosage is 0.2% to 38.9%. In addition, UL-94 test results show that 0.05%0.2% KSS can make 3.2mm thick sample up to UL-94 V - 0, but no matter how large the amount of l.6mm thick sample can not reach UL-94 V-0 grade, and KSS and PAPSQ, PVDF flame retardant polycarbonate 1.6mm thick sample can reach UL-94 V-0 class. It is shown from Figure 2 that sulfonate and fluoropolymer as well as siloxane and polycarbonate have good synergistic flame retardant effect.
According to the existing research, it can be considered that aromatic sulfonate can accelerate the carbon formation of polycarbonate and promote the crosslinking of polycarbonate, and siloxane can improve the thermal stability of polycarbonate and promote the formation of carbon. Fluoropolymer has a good inhibitory effect on the droplet formation of polycarbonate, and the synergistic mechanism between these three molecules is not clear yet, which needs further study.
In many polycarbonate soft PVC flame retardants, sulfonate system has the advantages of less addition and high efficiency, but it also has some defects, such as when used alone, can not meet some special products, such as thin-walled parts of the flame retardant requirements. It can be seen from the published literatures that adding some synergistic agents such as siloxane and fluoropolymer can further improve the flame retardancy of polycarbonate in polycarbonate. Therefore, the study on the compounding technology of sulfonate flame retardants will be the direction of research and development in the future.
Chlorinated paraffin and bromine chlorinated paraffin are widely used in the field of flame retardant. Chlorinated paraffins with a mass fraction of less than 40% are mainly used as plasticizers. Chlorinated paraffins with chlorine content of 50% - 70%, especially chlorinated paraffin -70, are widely used as additive flame retardants. Taking the formula reported in the literature as an example, the oxygen index of the sample can be up to 30 by adding DOP30, chlorinated paraffin -5020, Sb2O33 and other appropriate additives in 100 PVC.
But the flame retardant efficiency, chlorine flame retardants than brominated flame retardant (flame retardant elements such as inferior quality, chlorine flame retardant brominated flame retardant was only 50%), so in the past 20 years, some chlorine flame retardants for brominated flame retardants are replaced, as a kind of newly developed resistance in recent years, the burning of plasticizer - bromine - Chlorinated paraffin. Bromine chlorinated paraffin has high total halogen content (50% ~ 70%). It has excellent flame retardancy, plasticity and proper viscosity. It is compatible with many polymers and has low price and good development prospect.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
Polyvinyl chloride (PVC) products can be divided into two categories: hard and soft. The chlorine content of PVC reaches 56%, and its oxygen index is greater than 45. Therefore, hard PVC only needs further flame retardant in extreme cases.
The addition of 65 soft PVC flame retardants (100 phr PVC) in soft PVC to flammable ester plasticizers (such as phthalic acid, two formic acid, two octyl ester), the chlorine content can be reduced to 36%, and the oxygen index can be as low as 22. At the same time, soft PVC because of small hardness, can replace rubber in a certain occasion, so widely used in buildings, automobiles, cables and other flame retardant requirements of the industry, so soft PVC flame retardant is necessary. At present, there are many soft PVC flame retardants, including phosphate ester, chlorinated paraffin, three oxidation of two antimony, magnesium hydroxide (MDH), zinc borate, etc..
PPFBS is a soft PVC flame retardant for polycarbonate. The addition of 0.06%--0.1% PPFBS in polycarbonate can make the flame retardancy of the material reach UL-94V-0 (3.2mm thickness). It should be noted that the dosage of more than 0.1%, not only can not improve the flame retardant properties of the material, but also affect the transparency of polycarbonate.
In order to meet the higher flame retardant requirements, a small amount of siloxane can be used to make the compound. When the amount of siloxane is 0.02%--0.3% of the total amount of the formula, the flame retardancy of 1.6mm thick sample can reach UL-94V-0 grade. The most common use is poly (methyl phenyl siloxane), but some of the siloxane effects on the transparency of polycarbonate by PPFBS.
Studies have shown that viscosity is minus 6 square 1 x 10 to 3 x 10 4 negative m2 / S (20 C) of polymethylphenylsiloxane has a synergistic effect to the PPFBS, and the viscosity is 4 x 10 minus 6 square to 2 x 10 5 negative m2 / S (20 C), polymer molecular chain has more than two silicon atoms.
The price of PPFBS is higher, and PPFBS is replaced by partial KSS in practical application to reduce cost. For example, adding 0.02% PPFBS and 0.3% KSS in polycarbonate can make the material reach UL-94 V - 0 (1.6mm thick)
In the sulfonate soft PVC flame retardant used in polycarbonate: KSS is widely used, it does not contain halogen, environmental protection economy. Adding 0.05%--0.1% can increase the oxygen index of polycarbonate from 27% to 37%, and it will not affect the transparency of polycarbonate.
The deficiency is used alone can not meet the requirements of flame retardant high, such as thin-walled parts (not less than 2.5mm thickness) of the flame retardant level UL-94V-0. In practical application, it is often used in combination with polysiloxane. In addition, if a small amount of fluoropolymer is added at the same time, the flame retardancy of the material will be better. Among them, PAPSQ is poly (propyl / phenyl) silsesquioxane, and PVDF is polyvinylidene fluoride.
Tris(2-chloroethyl)phosphate(TCEP)
There Are Three Industrial Methods: Phosphorus Oxychloride And Chloroethanol Reaction; Phosphorus Trichloride And Chloroethanol Reaction Reoxidation; Phosphorus Oxychloride And Ethylene Oxide Reaction (Industrial Commonly Used Method).
1, Phosphorus Oxychloride And Ethylene Oxide To Sodium Metavanadate As A Catalyst, At 50 ° C Reaction, The Reaction By Neutralization, Washing, Vacuum Dehydration Off The Low Boiling, That Is, The Finished Product. Chlorohydrin Can Also Be Used As Raw Materials, And Phosphorus Oxychloride Or Phosphorus Trichloride Reaction To Produce Tris (2-Chloro Ethyl) Phosphate.
2, 326 Kg Of Phosphorus Oxychloride And 1.0 Kg Of Sodium Metavanadate Into The Reactor. The Nitrogen In The Autoclave Was Driven By Nitrogen, And 650 Kg Of Ethylene Oxide Was Introduced Under Vacuum And Stirred At 45 To 50 ° C For 2 To 3 Hours. Evaporation Of Excess Ethylene Oxide After Alkali Neutralization To Neutral, Washed, Vacuum Dehydrated. Finished Product.
3. Put Phosphorus Oxychloride And Sodium Metaphosphate Into The Reactor. Nitrogen To Drive The Air, In The Vacuum Under The Access To Ethylene Oxide, At 45 ~ 50 ℃ Stirring 2 ~ 3h. Evaporation Of Excess Ethylene Oxide After Alkali Neutralization To Neutral, Washed, Vacuum Dehydrated Finished.
Tris(2-chloroethyl)phosphate(TCEP)Use:
1. Tris (2-Chloroethyl) Phosphate Has Excellent Flame Retardancy, Excellent Resistance To Low Temperature And UV Resistance, The Steam Can Only Be Used At 225 ℃ Above The Direct Ignition Can Be Fired, But The Fire The Source Is Immediately Self-Extinguishing. This Product Is A Flame Retardant Not Only Can Improve The Material Level Of Flame Retardant Materials, But Also Improve The Flame Resistance Of Water Resistance, Acid Resistance, Cold Resistance And Antistatic Properties. Commonly Used In Flame Retardant Nitrocellulose And Acetate Fiber As The Substrate Of Paint Coatings, Unsaturated Polyester, Polyurethane, Acrylic, Phenolic Resin, Can Also Be Used For Soft PVC Plastic Flame Retardant. This Product Is Used For The Amount Of Unsaturated Polyester 10% To 20%, In The Polyurethane Rigid Foam (Flame Retardant Polyether As Raw Material) Can Be About 10% In The Soft PVC Used As Auxiliary Plastic Flame Retardant When The 5% To 10%. Flame Retardants, Uranium, Thorium, Plutonium, Technetium And Other Rare Metal Separation Solvent Or Extractant.
2. This Product Is Widely Used In Chemical Fiber Fabrics, Cellulose Acetate As A Flame Retardant, In Addition To Self-Extinguishing, But Also Improve Water Resistance, Cold Resistance And Antistatic Properties. The General Amount Of 5 To 10 Copies. This Product Is An Excellent Flame Retardant For Synthetic Materials, And Has A Good Role In The Promotion, Widely Used In Cellulose Acetate, Nitrocellulose Varnish, Ethyl Cellulose, Polyvinyl Chloride, Polyvinyl Acetate, Polyurethane, Phenolic Resin , In Addition To Self-Extinguishing Products, But Also Improve The Physical Properties Of Products, Products Feel Soft, Also Known As Oil Additives And Rare Elements Of The Extractant, And Flame Retardant Rubber Conveyor Belt Is The Main Flame Retardant Materials , The General Amount Of Added 5% To 10%.
3. Used As Additive Type Halogenated Phosphate Flame Retardant And Plasticizer. Molecules In Both Phosphorus And Chlorine, Flame Retardant Effect Is Remarkable, Not Volatile And Hydrolysis, Good Stability To Ultraviolet Light. Applicable To Phenolic Resin, Polyvinyl Chloride, Polyvinyl Acetate, Polyurethane And So On. Also Used As Nitrocellulose Coating Flame Retardant, PVC Flame Retardant Plasticizer, Metal Extractant, Gasoline Additives And Polyimide Processing Aids And So On. Can Improve Water Resistance, Weatherability, Cold Resistance, Antistatic Property. Reference Dosage 5% To 20%.
From Figure 2 a curve can be seen a small amount of KSS can be made of polycarbonate oxygen index increased significantly when adding 0.1% reaches a maximum value of 38.3%, then decreased; D line KSS and PAPSQ, PVDF display, flame retardant polycarbonate oxygen index is greatly improved, when the dosage is 0.2% to 38.9%. In addition, UL-94 test results show that 0.05%0.2% KSS can make 3.2mm thick sample up to UL-94 V - 0, but no matter how large the amount of l.6mm thick sample can not reach UL-94 V-0 grade, and KSS and PAPSQ, PVDF flame retardant polycarbonate 1.6mm thick sample can reach UL-94 V-0 class. It is shown from Figure 2 that sulfonate and fluoropolymer as well as siloxane and polycarbonate have good synergistic flame retardant effect.
According to the existing research, it can be considered that aromatic sulfonate can accelerate the carbon formation of polycarbonate and promote the crosslinking of polycarbonate, and siloxane can improve the thermal stability of polycarbonate and promote the formation of carbon. Fluoropolymer has a good inhibitory effect on the droplet formation of polycarbonate, and the synergistic mechanism between these three molecules is not clear yet, which needs further study.
In many polycarbonate soft PVC flame retardants, sulfonate system has the advantages of less addition and high efficiency, but it also has some defects, such as when used alone, can not meet some special products, such as thin-walled parts of the flame retardant requirements. It can be seen from the published literatures that adding some synergistic agents such as siloxane and fluoropolymer can further improve the flame retardancy of polycarbonate in polycarbonate. Therefore, the study on the compounding technology of sulfonate flame retardants will be the direction of research and development in the future.
Chlorinated paraffin and bromine chlorinated paraffin are widely used in the field of flame retardant. Chlorinated paraffins with a mass fraction of less than 40% are mainly used as plasticizers. Chlorinated paraffins with chlorine content of 50% - 70%, especially chlorinated paraffin -70, are widely used as additive flame retardants. Taking the formula reported in the literature as an example, the oxygen index of the sample can be up to 30 by adding DOP30, chlorinated paraffin -5020, Sb2O33 and other appropriate additives in 100 PVC.
But the flame retardant efficiency, chlorine flame retardants than brominated flame retardant (flame retardant elements such as inferior quality, chlorine flame retardant brominated flame retardant was only 50%), so in the past 20 years, some chlorine flame retardants for brominated flame retardants are replaced, as a kind of newly developed resistance in recent years, the burning of plasticizer - bromine - Chlorinated paraffin. Bromine chlorinated paraffin has high total halogen content (50% ~ 70%). It has excellent flame retardancy, plasticity and proper viscosity. It is compatible with many polymers and has low price and good development prospect.
Copyright: Zhang Jia Gang YaRui Chemical co.,Ltd
http://www.yaruichem.com
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