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China Patent > Textile Patent Fire Retardants Containing Phosphorus, Nitrogen, And Silicon And Used For Fabric Finish And Preparation Method Thereof Subject Fire Retardants Containing Phosphorus, Nitrogen, And Silicon And Used For Fabric Finish And Preparation Method Thereof Abstracts The Invention Discloses Fire Retardants Containing Phosphorus, Nitrogen, And Silicon And Used For Fabric Finish And A Preparation Method Thereof. The Fire Retardants Containing The Phosphorus, The Nitrogen, And The Silicon And Used For The Fabric Finish Comprise, By Mass, 100-400 Parts Of Solvents, 100 Parts Of I Type Active Phosphides And 30-500 Parts Of Chemical Compounds Containing Phosphonium And Silicon Reacted From Silane Coupling Agents Containing Epoxy Groups. 10-30 Parts Of Nitrogen-Containing Compounds Are Added To The 100 Parts Of Chemical Compounds Containing Phosphonium And Silicon, And The Fire Retardants Containing Phosphorus, Nitrogen, And Silicon Can Be Obtained After Stir Of The Nitrogen- Containing Compounds And The Chemical Compounds Containing Phosphonium And Silicon, Or Under The Temperature Of 130-180 DEG C, By Mass, 5-10 Parts Of Solvents Is Added, 100 Parts Of II Type Active Phosphides Is Stirred Evenly With 30-500 Parts Of Silane Coupling Agents Containing Epoxy Groups, And Chemical Compounds Containing Phosphonium And Silicon Can Be Obtained Through The Reaction Between The II Type Active Phosphides And The Silane Coupling Agents Containing

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China Patent>Textile PatentFire Retardants Containing Phosphorus, Nitrogen, And Silicon And Used For Fabric Finish And Preparation Method Thereof

SubjectFire Retardants Containing Phosphorus, Nitrogen, And Silicon And Used For Fabric Finish And Preparation Method ThereofAbstractsThe Invention Discloses Fire Retardants Containing Phosphorus, Nitrogen, And Silicon And Used For Fabric Finish And A Preparation Method Thereof. The Fire Retardants Containing The Phosphorus, The Nitrogen, And The Silicon And Used For The Fabric Finish Comprise, By Mass, 100-400 Parts Of Solvents, 100 Parts Of I Type Active Phosphides And 30-500 Parts Of Chemical Compounds Containing Phosphonium And Silicon Reacted From Silane Coupling Agents Containing Epoxy Groups. 10-30 Parts Of Nitrogen-Containing Compounds Are Added To The 100 Parts Of Chemical Compounds Containing Phosphonium And Silicon, And The Fire Retardants Containing Phosphorus, Nitrogen, And Silicon Can Be Obtained After Stir Of The Nitrogen-Containing Compounds And The Chemical Compounds Containing Phosphonium And Silicon, Or Under The Temperature Of 130-180 DEG C, By Mass, 5-10 Parts Of Solvents Is Added, 100 Parts Of II Type Active Phosphides Is Stirred Evenly With 30-500 Parts Of Silane Coupling Agents Containing Epoxy Groups, And Chemical Compounds Containing Phosphonium And Silicon Can Be Obtained Through The Reaction Between The II Type Active Phosphides And The Silane Coupling Agents Containing Epoxy Groups. 10-30 Parts Of Nitrogen-Containing Compounds And 5-20 Parts Of Emulsifiers Are Added To 100 Parts Of Chemical Compounds Containing Phosphonium And Silicon, And The Fire Retardants Containing Phosphorus, Nitrogen, And Silicon Can Be Obtained After Stir Of The Nitrogen-Containing Compounds, The Emulsifiers And The Chemical Compounds Containing Phosphonium And Silicon. The Synthetic Method Of The Fire Retardants Containing The Phosphorus, The Nitrogen, And The Silicon And Used For The Fabric Finish Is Simple, High In Efficiency, Low In Toxicity And Environment-Friendly. After The Fire Retardants Are Finished On Fabrics, The Fabrics Can Have Good Fire Retardant Property.ExplanationAn Apparatus For Fabric Finishing Phosphorus, Nitrogen, Silicon Flame Retardants And MethodTechnology[0001] The Present Invention Relates To A Flame Retardant, In Particular To A Method For Finishing Fabrics Phosphorus, Nitrogen, Silicon Fire Retardant And Its Preparation Method. The Flame Retardants Can Be Applied To Cotton, Polyester And Other Fabric Finishing, Compared With Conventional Flame Retardants, Synthetic Method Is Simple, Efficient And Low Toxicity Environmentally Friendly.Technical Background[0002] With The Social Development And The Improvement Of Living Standards, The Use Of Textiles And Consumption Is Increasing. Due To Fires Caused By Ignition Of Textiles Is Increasing, Resulting In Loss Of Life And Property, So To Improve The Flame Retardancy Of Textiles Is Essential. Fabrics Used Are Halogenated Flame Retardants (Including Brominated And Chlorinated), Phosphorus, Nitrogen And Silicon System. Halogen-Containing Flame Retardant Effect Is Remarkable. However, Due To Halogenated Flame Retardants Damage To The Environment, And Its Application Is Limited. Containing Only A Single Component Of The Phosphorus, Nitrogen And Silicon-Based Flame Retardants And Flame Retardant Is Not Ideal, It Is Difficult To Meet The Application Requirements. Therefore, The Composite Type Flame Retardant Halogen-Free Flame Retardants To Become The Development Direction.[0003] Phosphorus, Nitrogen, Silicon, Flame Retardant, High Efficiency, Low Toxicity, Environmentally Friendly. When The Phosphorus, Nitrogen And Silicon Flame Retardants When Used Under High Temperature, Thermal Decomposition Of The Nitrogen Release Of Nonflammable Gas, Dilute The Combustible Gases And Take A Lot Of Heat Effect, Thereby Reducing The Surface Temperature Of The Polymer, Combustion Is Inhibited. Phosphorus Flame Retardant Mechanism Due To Its Solidification And Partial Vapor Phase Flame Retardant Mechanism, In The Process Of Flame-Retardant Materials Can Not Only Reduce Heat Release Rate, Improve Flame Retardant Effect, But Also Break Down Into Acid Pyrophosphate Or Promote Charring. These Carbon Layer Of Silicon To Increase The Stability And Have Some Smoke Suppression Effect. Phosphorus, Nitrogen, Silicon Flame Retardants Has Important Application Value. Currently, The Preparation Of Phosphorus-Containing Silicon Compounds, Mainly The Following:[0004] (I) Using Phosphorus Oxychloride, Phosphorus Pentoxide, Or An Isocyanate As A Raw Material, With A Hydroxy Silicone Oil, Silicone, Etc. Prepared By The Reaction Of Phosphorus-Silicon-Containing Flame Retardants. However, Due To Strong Reactivity Of Phosphorus Oxychloride, Poor Stability, Easy Hydrolysis Reaction Will Produce HCl Byproduct, To Protect The Environment, The Need For Subsequent Processing. Pentoxide Corrosive Big Isocyanate Is Highly Toxic And Are Not Directly Touch In The Preparation Process Requires Special Protection Measures, Higher Production Costs, And Not Suitable For Flame-Retardant Fabric.[0005] (2) Using The PH Bond-Containing Compound And A Double Bond-Containing Silane Or A Radical Reaction By The Addition Reaction, Synthesis Of Phosphorus-Containing Organic Silicon Compound. Synthesis Method By An Addition Reaction Of Long Reaction Time, Total Reaction Time Of About 16-40 Hours. Synthesis By Radical Emulsion Prepared By The Method Requires, Breaking And Other Processes, Process Complexity, High Production Costs, And The Resulting Product Is Water-Insoluble Solids, Not Suitable As A Fabric Finishing Agent.[0006] (3) The Hydroxyl Group-Containing Siloxane And An Active Phosphorus Compound By Transesterification, Synthetic Phosphorus Flame Retardant Silicone Homogeneous U. Since The Transesterification Reaction Is A Reversible Reaction, The Conversion Rate Is Difficult To Control, Bring Some Inconvenience To The Synthesis.[0007] The Flame Retardant Used In Textile Finishing And Application Of The Requirements Of The Flame Retardants In Rubber, Plastics Are Different, Mainly Reflected In Two Aspects: (1) Flame Retardant Fabric Finishing Agent Requests Can Be Dissolved In Water Or By Simply Soluble In Water Emulsion, Dubbed Finishing The Working Fluid, And Then Finishing By Way Of Padding To The Fabric. The Prior Art Silicon-Phosphorus Flame Retardant Used For Rubber, Plastic, Product And More Solid Or Insoluble Liquid, Not Suitable For Fabric Finishing. Some Of The Silicone Oil And Phosphorus-Containing Epoxy Compound, The Synthesis Of Phosphorus-Silicon Emulsion As Fabric Finishing Agents. This Method, However Complex Process, Time-Consuming, Need To Chlorine Molybdate As A Catalyst, The Price Is Expensive, The Solvent Is Benzene, Toluene, Xylene, Chloroform, Etc., Toxicity, High Requirements For Post-Processing. (2) Fabric Unlike Plastics, Rubber, Fabrics Washed In Use Needs. Therefore, Flame Retardant Fabric And Fabric Finishing Agents Need To Have A Certain Combination Of Fastness To Ensure Washable Fabric Flame Retardant Functions. Hydroxy Silicone Oil Was Used, Phosphorus Oxychloride And Two Fatty Amine, Synthesis Of A Plurality Of Hydroxyl-Containing Flame Retardant, So That It Can Bind Strongly To The Fabric. However, The Reaction Of Phosphorus Oxychloride, And The Reaction Emit Hydrogen Chloride Gas, To Protect The Environment, The Need For Subsequent Processing, And The Complicated Synthesis, The Need To Protect The Hydroxy-Protecting Hydroxyl Reconciliation Process, Not Easy Production Applications.[0008] Therefore, For Fabric Finishing, Develop A Synthetic Process Is Simple, Environmentally Friendly And Efficient Flame Retardant Fabric Finishing Agent Is Necessary.

SUMMARY OF THE INVENTION

[0009] The Present Invention Aims To Prepare Phosphorus, Nitrogen, Silicon Flame Retardant, The Flame Retardant, Low Toxicity, So Finishing The Fabric, Giving The Fabric Excellent In Flame Retardant Effect, It Is Also A Good Washing Sex.[0010] The Present Invention Is An Active Phosphorus Compound And A Silane Coupling Agent Containing An Epoxy Group Ring-Opening Polymerization To Obtain A Phosphorus-Containing Silicon Compound, The Compound Obtained By Mixing The Compound With A Nitrogen-Containing Phosphorus, Nitrogen And Silicon Flame Retardants . Through A Phosphorus, Nitrogen And Silicon, Synergy, To Provide Better Flame Retardant Fabric.[0011] The Present Invention Dori Achieved Through The Following Technical Solution:[0012] The Present Invention A Method For Finishing Fabrics Phosphorus, Nitrogen And Silicon Flame Retardant Preparation Method Comprises The Following Steps:[0013] (I) Synthesis Of Phosphorus-Containing Compound: In The Container Through An Inert Gas For 3-10 Minutes At Room Temperature, Total Parts By Mass, Adding 100-400 Parts Of The Solvent, 100 Parts Of I-Type Activity Phosphite And 30-500 Parts Of An Epoxy Group-Containing Silane Coupling Agent, A Continuous Mechanical Stirring, The Reaction 1-7 Hours, The Solvent Was Removed Under Reduced Pressure And The Low Boiling, Ie Phosphorus-Containing Compound; Said Epoxy Group-Containing The Silane Coupling Agent Is 3 - Glycidoxypropyl Methyldiethoxysilane, 2 - (3,4 - Epoxy Cyclohexyl) Ethyl Baby Burn Dimethoxy 2 - (3 4 - Burning Epoxycyclohexyl) Ethyl Diethoxy Baby Burn, Y_ (2,3 - Epoxypropoxy) Propyl Trimethoxy Silane, Epoxy, Cage Silsesquioxane In One Or More Of; Said Phosphite Type I Activity As Phosphoric Acid, Phosphorous Acid, Hypophosphorous Acid In One Or More Of; Said Solvent Is Water, Ethanol, Isopropyl Alcohol, Methanol In One Or More Of ;[0014] (2), Phosphorus, Nitrogen, Silicon Flame Preparation: In The Vessel, 100 Parts Of Said Phosphorus-Containing Compound, And 10-30 Parts Of A Nitrogen-Containing Compound, A Continuous Mechanical Stirring For 3-5 Minutes, Mixture Containing Phosphorus, Nitrogen And Silicon Flame Retardant; The Nitrogen-Containing Compound Is Urea, Ammonia, Triethanolamine, Diethanolamine, In One Or More Of Dicyandiamide.[0015] Preferably, The Inert Gas Is Nitrogen; Or Said Inert Gas Is Argon, Helium, And Neon In One. The Epoxy Group-Containing Silane Coupling Agent Of 100-200 Copies.[0016] The Present Invention Is Used For Fabric Finishing Second Phosphorus, Nitrogen And Silicon Flame Retardant Preparation Method Comprises The Following Steps:[0017] (I) Synthesis Of Phosphorus-Containing Compound: In The Container Through The Inert Gas Is 3-10 Minutes At 130_180 C, The Total Parts By Mass, Adding 5-10 Parts Of Solvent, 100 Parts Of Type II Activity Phosphides With 30-500 Parts Of An Epoxy Group-Containing Silane Coupling Agent, Stir The Reaction 1-7 Hours, The Solvent Was Removed Under Reduced Pressure And The Low Boiling, Ie Phosphorus-Containing Compound; Said Solvent Is Water, Ethanol, Isopropanol, Methanol, One Or More Of; Said Phosphite Type II Activity Of 9,10 - Dihydro-9 - Oxa-10 - Phosphaphenanthrene-10 - Oxide (Abbreviated D0P0) , Diethyl Phosphite, Dibutyl Phosphite, Dimethyl Phosphite In One Or More Of; Wherein The Epoxy Group-Containing Coupling Agent Burn Baby Stuffed 3_ Glycidoxy Propyl Methyl Base _ Ethoxy Baby Burn 2 - (3,4 - Epoxycyclohexyl) Ethyl Trimethoxysilane 2 - (3,4 - Epoxycyclohexyl) Ethyltriethoxysilane Silane, -(2,3 - Epoxypropoxy) Propyl Trimethoxysilane, Epoxy Group Silsesquioxane Cage In One Or More Of;[0018] (2), Phosphorus, Nitrogen, Silicon Flame Preparation: In The Vessel, 100 Parts Of Said Phosphorus-Containing Compound, 10 To 30 Parts Of A Nitrogen-Containing Compound, And 5-20 Parts Of An Emulsifier, A Continuous Mechanical Stirring 3-5 Minutes To Obtain A Phosphorus, Nitrogen, Silicon Flame Retardant; Nitrogen-Containing Compound Is Urea, Ammonia, Triethanolamine, Diethanolamine, In One Or More Of Dicyandiamide; The Emulsifying Agent Is An Alcohol Isomers Ten Polyoxyethylene Ether, Polyoxyethylene Tridecyl Alcohol Isomeric Ethers, Polyoxyethylene Isomeric Polyoxypropylene Ether, A Straight-Chain Fatty Alcohol Ethoxylates In One Or More Of.[0019] Preferably, The Inert Gas Is Nitrogen; Or Said Inert Gas Is Argon, Helium, And Neon In One. The Epoxy Group-Containing Silane Coupling Agent Of 100-200 Copies.[0020] The Present Invention Is A Method For Finishing Fabrics Phosphorus, Nitrogen, Silicon Flame Retardant, By The Method Described In Any Of The Above.[0021] The Present Invention Over The Prior Art Has The Following Advantages:[0022] 1, The Invention First With The Reactive Epoxy Group-Containing Phosphorus Compound And A Silane Coupling Agent To Synthesize Phosphorus-Containing Compound. The Compound Containing S1-O-CH3, While When Finishing The Fabric, S1-O-CH3 Hydrolyzed To Form A Silanol Bond, With The Fabric Between The Fiber Surface And The Dehydration Condensation To Form A Covalent Bond Firmly Bonded To The Fiber Surface To Improve The Functionality Of Washable Fabric Flame Retardant;[0023] 2, The Present Invention Is Directed To The Synthesis Of Phosphorus-Containing Compound And A Nitrogen-Containing Compound Is Mixed Baby Obtain Also Contain Phosphorus, Nitrogen, Baby Three Kinds Of Flame Retardant Elements, Through A Phosphorus, Nitrogen And Silicon Flame Retardant Synergist Effect, Greatly Improving The Flame Retardancy Of The Fabric;[0024] 3, The Flame Retardant Of The Present Invention Directly Or Through A Simple Water-Soluble Emulsification Process, Suitable For The Fabric Flame Retardant;[0025] 4, The Present Invention Is Inexpensive Method Of Synthesis Of Raw Materials, And The Toxicity, The Practical Application Of Safety, Does Not Require Special Equipment;[0026] 5, The Invention Process Is Simple, Short Reaction Time, Easy Operation, Low Production Costs.BRIEF DESCRIPTION[0027] Figure 1 Is Phosphorus In Example 1 Of The IR Spectrum Of The Silicon-Containing Compound;`[0028] Example 2 Figure 2 Is A Phosphorus Containing Compound In The Infrared Spectrum;[0029] Figure 3 Is A Third Embodiment The Phosphorus-Containing Compound Of The Infrared Spectrum;[0030] Example 4 Figure 4 Is A Phosphorus-Containing Compound In The Infrared Spectrum;[0031] Example 5 Figure 5 Is A Phosphorus-Containing Compound In The Infrared Spectrum;[0032] Example 6 Figure 6 Is A Phosphorus-Containing Compound In The Infrared Spectrum.Specific Embodiments[0033] The Following Accompanying Drawings And Embodiments Of The Present Invention Will Be Further Described, But The Present Invention Is Not Limited To The Scope Of The Claimed Range Table Does Embodiment.[0034] Example 1[0035] (I) Synthesis Of Phosphorus-Containing Compound[0036] In The Container Under Nitrogen For 4 Minutes At Room Temperature, Added IOOg Water, IOOg 248g3_ Glycidoxypropyl Acid And Methyl Diethoxy Silane, Continuous Mechanical Stirring, The Reaction I Hour, Evaporated Under Reduced Pressure Removal Of Solvent And Low Boiling, SP Phosphorus Containing Compound Obtained. The Phosphorus-Containing Compound For Infrared Analysis, Shown In Figure 1, 763 011 ^ 9450 ^ 1 Epoxy Group Characteristic Absorption Peak Disappears, 1018cm-1 Very Broad Peak Of The Characteristic Absorption Peak Of POC, 1112 ^ 1 Is Silicon Characteristic Absorption Peak Oxygen Bond. Thus, Phosphoric Acid, And 3 - Glycidoxypropyl Methyl Diethoxy Silane Reaction Between.[0037] (2), Phosphorus, Nitrogen, Silicon Preparation Of Flame Retardant[0038] In The Vessel IOOg Phosphorus Containing Compound And 22.3g Urea, At Room Temperature Under Continuous Mechanical Stirring For 5 Minutes To Obtain A Phosphorus, Nitrogen And Silicon Flame Retardants.[0039] (3) Fabric Finishing [0040] The Above Phosphorus, Nitrogen And Silicon Flame Retardant Dissolved In Water, The Concentration Is Controlled To 300g / L, To Obtain, After Finishing The Working Fluid, Respectively, For Finishing Of Cotton, Polyester Fabric . Specific Process: A Dip A Rolling, Rolling Over Rate: 70% -80%, 85 C Drying 5min, 170 C Curing 3min. Press FZ/T01028-1993 (Textile Fabrics - Burning Level Performance Measurement Method) Method To Test Its Flame Retardant Properties. The Results Shown In Table I:[0041] Table I The Flame Retardancy Of The FabricDRAWINGSClaimsA Method For Fabric Finishing Phosphorus, Nitrogen, Silicon Preparation Of Flame Retardant, Characterized By Comprising The Steps Of: (1) Synthesis Of Phosphorus-Containing Compound: In The Container Through The Inert Gas 3 Is - For 10 Minutes At Room Temperature, Total Parts By Mass, Adding 100-400 Parts Solvent, 100 Parts Of I-Type Activity And 30-500 Parts Phosphide Silane Coupling Agent Containing An Epoxy Group, A Continuous Mechanical Stirring, The Reaction 1-7 Hours, The Solvent Was Removed Under Reduced Pressure And The Low Boiling, Ie Phosphorus-Containing Compound; Said Epoxy Group-Containing Silane Coupling Agent Is 3 - Glycidoxy-Propyl Methyl Diethoxy Silane, 2 - (3,4 - Epoxy Cyclohexyl) Ethyl Baby Burn Dimethoxy 2 - (3, 4 - Epoxycyclohexyl Burn Yl) Ethyl Diethoxy Baby Burn, Y - (2 3 - Glycidoxypropyl) Trimethoxysilane, Epoxy Group Silsesquioxane Cage In One Or More Of; Said Phosphite Type I Activity As Phosphoric Acid, Phosphorous Acid, Hypophosphorous Acid In One Or More Of; Said Solvent Is Water, Ethanol, Isopropyl Alcohol, Methanol In One Or More Of; (2), Phosphorus, Nitrogen, Silicon Preparation Of Flame Retardant: 100 Parts Of The Vessel, The Phosphorus-Containing Compound, And 10-30 Parts Of A Nitrogen-Containing Compound, Continuous Mechanical Stirring For 3-5 Minutes To Obtain A Phosphorus, Nitrogen, Silicon Flame Retardant; The Nitrogen-Containing Compound Is Urea, Ammonia, Triethanolamine, Diethanolamine , In One Or More Of Dicyandiamide.(2) As Claimed In Claim 1, Wherein The Fabric Finishing Phosphorus, Nitrogen, Silicon Preparation Of Flame Retardant, Characterized In That: Said Inert Gas Is Nitrogen; Or Said Inert Gas Is Helium Gas, Neon Gas And Argon Gas In One.3 According To Claim 1, Wherein The Fabric Finishing Phosphorus, Nitrogen, Silicon Preparation Of Flame Retardant, Wherein: Said Epoxy Group-Containing Silane Coupling Agent Of 100-200 Copies.4 A Method For Fabric Finishing Phosphorus, Nitrogen, Silicon Preparation Of Flame Retardant, Characterized By Comprising The Steps Of: (1) Synthesis Of Phosphorus-Containing Compound: Inert Gas In The Container Through 3-10 Minutes At 130-180 C Under The Total Parts By Mass, Adding 5-10 Parts Of Solvent, 100 Parts II And 30-500 Parts Of Reactive Phosphide Containing An Epoxy Group-Containing Silane Coupling Agent, Stir To React For 1 -7 Hours, Evaporated Under Reduced Pressure To Remove The Solvent And Low Boiling, Ie Phosphorus-Containing Compound; Said Solvent Is Water, Ethanol, Isopropyl Alcohol, Methanol In One Or More Of; Said Type II Reactive Phosphorus Compounds Of 9,10 - Dihydro-9 - Oxa-10 - Phosphaphenanthrene-10 - Oxide, Dimethyl Phosphite, Diethyl Phosphite, Dibutyl Phosphite In One Or More; The Epoxy Group-Containing Silane Coupling Agent Is 3 - Glycidoxypropyl Methyldiethoxysilane, 2 - (3,4 - Epoxy Cyclohexyl) Ethyl Dimethoxy Baby Burn, 2 - (3, 4 - Epoxycyclohexyl Burn Yl) Ethyl Diethoxy Baby Burn, Y - (2, 3 - Glycidoxypropyl) Trimethoxysilane, Epoxy Group Cage Silsesquioxane Shape In One Or More Of; (2), Phosphorus, Nitrogen, Flame Retardant Wa Prepared: In The Vessel, 100 Parts Of Said Phosphorous-Containing Compound, 10 To 30 Parts Wa Nitrogen-Containing Compound And 5 To 20 Parts Of An Emulsifier, Continuous Mechanical Stirring 3-5 Minutes To Obtain A Phosphorus, Nitrogen, Silicon Flame Retardant; Nitrogen-Containing Compound Is Urea, Ammonia, Triethanolamine, Diethanolamine, Dicyandiamide In One Or More Of Kind; Said Emulsifier For Heterogeneous Ten Alcohol Ethoxylates, Polyoxyethylene Tridecyl Alcohol Isomers Ethers, Isomers Polyoxyethylene Polyoxypropylene Ether, Straight-Chain Fatty Alcohol Ethoxylates One Or Variety.5 As Claimed In Claim 4 For Fabric Finishing Phosphorus, Nitrogen, Silicon Preparation Of Flame Retardant, Characterized In That: Said Inert Gas Is Nitrogen; Or Said Inert Gas Is Argon Gas, Helium And Neon Gas In One.As Claimed In Claim 1, Wherein The Fabric Finishing Phosphorus, Nitrogen, Silicon Preparation Of Flame Retardant, Wherein: Said Epoxy Group-Containing Silane Coupling Agent Of 100-200 Copies.7 A Method For Fabric Finishing Phosphorus, Nitrogen, Silicon Flame Retardant, Characterized In That: The Any One Of Claims 1-6 Prepared By The Method.Document NumberD06M101/32GK103161074SQ201310044814Application Date2013619 Application Date: 201324 Priority Date: 201324Inventor, , Applicant: ,

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http://link.springer.com/article/10.1007%2Fs11595-009-2235-9 Journal of Wuhan University of Technology-Mater. Sci. Ed.April 2009,Volume 24,Issue 2,pp 235-240Date: 09 Jul 2009Effect of flame retardant containing phosphorus and silicone on thermal performance of PC/ABS Ping Wei , Dan Wu, Hanfang Zhong, Jianxin DuAbstractA flame retardant (DPA-SiN) containing phosphorus, nitrogen and silicon elements was synthesized. The halogen free flame retardant was incorporated into PC/ABS to improve its flame retardancy. The flame-retardant properties of the PC/ABS/DPA-SiN blends were estimated by limiting oxygen index (LOI) values and CONE Calorimeter, while thermal stabilities were investigated through thermo gravimetric analysis (TGA). The PC/ABS/DPA-SiN blends were thermally degraded at 400 C for different amounts of time and studied by Fourier transform infrared spectroscopy (FTIR) to better understand the degradation behavior of PC/ABS/DPA-SiN.Funded by Shanghai Science and Technology Commission of China (No. 05dz22303)

Industry NewsLocationHome>>News>>Industry NewsGreen flame retardants used in the textile fabricsA green flame IntroductionEnvironmental problems is one of the central problems facing humanity today's world, the current deterioration of the global environment has a clear threat to human survival. According to incomplete statistics, the world's current production of chemicals or use of up to 10 million species, only the US chemical industry would discharge more than 30 million tons per year of chemical waste into the environment.Green chemistry is the raw material of atoms in molecules hundred percent into the product, do not generate by-products or waste generated or less, and waste of "zero discharge" of a chemical production process that has non-toxic materials, conversion rate environment-friendly characteristics.Green flame retardants from its design, material selection, color design, all aspects of the process to save, use and waste disposal, and other products have to comply with the concept of green chemistry, that minimize or abolish those on human health, environment, safety of hazardous materials and production processes of the use of social, not the people's safety and environmental pollution at the expense of materials to improve flame retardant effect, so it truly retardant materials to prevent contamination from the source.2 types of green flame retardantsThe role of fire retardant fabric material is to reduce the chance of fire and slow the rate of flame spread. Increased demand for flame retardants in people at the same time, the flame retardant performance requirements are more multi-faceted. Green flame itself in the production and use of the process should be non-toxic, it should have good thermal stability, resistance to aging, light stability, non-corrosive, at the same time, it should be low smoke and low toxicity of combustion products . At present, many types of green flame retardants, according to the chemical composition, structure and composition of flame retardant mechanism can be divided into non-halogen flame retardant polymer nano / inorganic composite flame retardants, inorganic flame retardants and intumescent flame retardant .2.1 halogen flame retardant2.1.1 phosphorus flame retardantRetardant mechanism phosphorus flame retardant is mainly generated polyvinylidene decompose phosphate phosphorus compounds when heated. Stable non-volatile compound is polyvinylidene phosphate, the combustion surface of the spacer layer is formed. In addition, phosphorylation of dehydration due to polyvinylidene promote carbonization, charring the surface to form a film, which play a role in flame [1-2]. Phosphorus flame retardant polymer burning, less environmental pollution, flame retardant content is less able to achieve good results, and a small variety of effects on the performance of polymeric materials, has been widely used. However, phosphorus-based flame red phosphorus hygroscopic hydrolysis and emit toxic phosphine, and organophosphorus flame retardants are also large amount of smoke, toxic, easily hydrolyzed, defects and poor thermal stability.Current red phosphorus modification treatment is the most effective method for surface coating [3-5]. And for phosphorus flame retardants easily hydrolyzed, defects and poor thermal stability, phosphate ester flame retardants developed gradually from a single to a double poly phosphate ester flame retardants or polyphosphate development. Yuan love, etc. [6-7] with phosphorus oxychloride, resorcinol and phenol for the synthesis of tetraphenyl resorcinol diphosphate; Liu Fan et al. [8] The solvent-free synthesis of washable cotton fabrics flame retardant phosphorus N- methyl-3-dimethyl propionamide.Ammonium polyphosphate (APP) is another important phosphorus-based flame retardants, methods for their preparation are many [9-10], but most of the methods for preparing the products that can be poor in water resistance. Synthesis of long-chain water-soluble APP is the main way to resolve, there are two ways, first by adding phosphoric acid or phosphate agent for control of process conditions ammoniated water-soluble polymer produced APP [11-12]; the second is through the APP other crystal preparation easier conversion to produce water-soluble type APP [13-15].2.1.2 metal hydroxide flame retardantAluminum hydroxide and magnesium hydroxide are the main varieties of metal hydroxide flame retardants, which presence of toxic smoke, corrosive, low price, good thermal stability and other characteristics, known as pollution-free flame retardants. They absorb heat due to thermal decomposition of the burning zone, the temperature of combustion combustion zone is reduced to below the critical temperature of combustion, combustion self-extinguishing, after decomposition of metal oxides most high melting point, good thermal stability, covering the burning solid surface blocking heat conduction and thermal radiation, and thus play a flame retardant, heat generated by the water absorption of the latent heat of evaporation of further lowering the temperature, and produce large amounts of water vapor, diluting the flammable gas also play a flame retardant.Aluminum hydroxide, magnesium hydroxide ultrarefined, and subjected to surface modification treatment with an organic silane coupling agent or a fatty acid, it can be quickly dispersed in a resin integrally, thereby reducing the flame propagation speed, so that when the smoke produced by combustion amount, the amount of toxic gases and corrosive gases amounts are quite small, greatly improving its flame and smoke suppression effect.2.2 IFRIntumescent flame retardant (IFR system for short) is a phosphorus, nitrogen, carbon is the main core components retardant intumescent flame retardants are usually composed of carbon source, acid source and foaming source of three parts. Under the action of flame and heat, acid source heat release of inorganic acids, polyol ester, then dehydration carbonization reaction of water vapor as well as some non-combustion gas to inflate the carbon layer, forming an extra layer of microporous carbon tough foam layer, the resulting melt can be adsorbed on the carbon layer, the surface of the fire, heat and oxygen barrier to the entry of the carbonaceous layer having oxygen barrier and heat transfer and smoke suppression effects, and can prevent the combustion process produces molten drops, effectively prevented the spread of flames caused salivation, so as to achieve the purpose of flame and smoke, toxic, non-corrosive gases [16]. Therefore, the expansion flame retardant technology has become one of the most active areas of current research flame. Expandable graphite which is a special intumescent flame retardant. The flame retardant without dehydrating acid source, at a high temperature, heat expandable graphite intercalation layer easily decomposed, generated gas so that the rapid expansion of the graphite layer spacing of tens to hundreds of times. When expandable graphite is mixed with the polymer, under the action of flame, expandable graphite to form a tough layer of carbon on the surface of the polymer, which play the role of fire.2.3 inorganic flame retardants2.3.1 silicon-based flame retardantsSilicone flame retardants in recent years to develop a new type of high efficiency, low toxicity, anti-droplet, environment-friendly halogen-free flame retardants, but also a char type smoke suppressant, it gives excellent resistance polymer burning smoke suppression, while also improving the processing performance of materials and improve the mechanical strength of the material, especially low-temperature impact strength [17]. These silicon material effect either alone, or mixed with the polymer as copolymer are promising flame retardants. In the presence of a metal hydroxide, a silica gel is reacted with an organic alcohol to generate a variety of organic silicide. Polyhydroxy polymer with the additive effect of the combustion process such as silica gel, cross-linked polymers will result occurs, thereby forming Si-O-C type protective char layer.With the growing environmental awareness, silicon-based flame retardants and silicon-based composites will be one of the future research and development of green flame of the main trend.2.3.2 boric acid-based flame retardantsZinc borate is an effective, versatile flame retardant, smoke suppressant. It contains crystal water, in the flame, the water is released, to absorb heat, less heat required for flame spread and dilute the oxygen content. Zinc borate can also work with other metal compounds formed in the surface of the molten material of the spacer layer borate, and borate-forming skeleton, play a very good oxygen barrier effect.2.4 Nano-polymer / inorganic composite fireNanocomposite material refers to one or more components to nanometer size or molecular level are uniformly dispersed in a matrix of another component, its study only 10 years of history. However tests show that the presence of its ultrafine size, the nature of the various types of nanocomposites are greatly improved than the corresponding macro or micro-scale composite materials, thermal stability and flame retardant properties of the material also has a larger magnitude increase [18].Some can be broken into scaly inorganic nano-sized micro-structure, its lamellar spacing is generally a few tenths to a few nanometers, which not only allows certain polymers embedded in the interlayer space in its nano-sized form. "embed nanocomposites ", such as montmorillonite (MMT) are Si-O tetrahedral and octahedral Al-O 2: 1 type clay minerals close-packed structure, the polymer / montmorillonite nano composite material thermal stability increased the reason is not only embedded polymer special "sandwich" structure, and thermal degradation and related energy and ion polarity. That is, the "embedded polymer" is not only to improve the thermal stability of its special structure, but also with "lying" in between the layers of montmorillonite steric polymer segment is restricted so that the thermal motion of the relevant [19].DuJX such as X-ray photoelectron spectroscopy (XPS) polystyrene (PS) / clay nanocomposites and polymethyl methacrylate (PMMA) / clay nano thermal degradation and flame retardant mechanism of the composites were studied. By XPS analysis, when the sample to thermal degradation, the oxygen content of the sample surface will be increased, while the carbon content will decrease, which is the amount of the sample surface to reduce the polymer content and a corresponding increase in the silicate sake. Meanwhile, at 200 ~ 250 MMT will decompose to form Al2O3 and SiO2, and SiO2 due to its low surface energy focused on the sample surface, a phenomenon in embedded, exfoliated and embedding - stripping hybrid nanocomposite materials are similar [20-21].Researches on polymer / layered inorganic nanocomposites very active [22-24]. The use of porous or layered inorganic compound properties, nano-composite material of artificial microstructures in polymer formation in the combustion process of thermal decomposition, carbon and inorganic salts may form a multi-layer structure, it functions as an insulator and prevent combustible gases escape a role. Since this is from the nano or molecular level up to consider structural design of polymer composite materials, so that its flame retardancy and mechanical properties are improved, so this type of fire-retardant material is a promising green halogen-free additives.3 green flame retardants used in textilesWith the development of technology, people for textile safety performance requirements are also increasing, textile flame safety performance has become an important indicator of the international textile testing, and domestic fire safety testing requirements are also increasing attention. In addition to using the essence of flame retardant fabric, such as Kevlar, nitrile cotton, , Nomex, Australia PR97, etc., finishing retardant fabric has also been heavily used in the process, the use of greener flame retardant safety flame retardant textile finishing textiles States are becoming increasingly accepted by the market. These green flame is applied not only to those special types of clothing, such as welders clothing, fire service, can also be applied daily textile fabrics, such as home decor and bedding fabrics, military supplies and automotive component materials are also widely used in the retardant textiles. Therefore, safe, green, feel good flame retardants will increase market share.Ciba's FlamesrabNOR116 melt process is non-halogen flame retardant for polyolefin-based fibers, including non-woven material, exhibit excellent flame retardant performance, can be used extensively for a variety of automotive and construction structural materials. The company's products due to improved flame resistance to ultraviolet (UV) stability in outdoor fabrics and industrial applications have developed.Metal hydroxide flame retardant, flame-retardant carpet styrene - butadiene latex aluminum hydroxide, when the combustion can be substantial absorption of heat, and therefore at the beginning of combustion of the flame retarding effect is also very significant.Apexicial company recently launched a non-halogen, high phosphorus soluble fusion (meltsoluble) flame retardants --ApexicialPyrapex, polyester and nylon fabric that can be used, because of its soluble polymer melt, in particular by the need to protect the twin flame group points nonwovens producers welcome.Intumescent flame retardant (IFR) is a kind of nitrogen and phosphorus flame retardant composite main components, mainly in two ways when applied to fibers and fabrics: First formulated as a flame retardant finishing solution, by coating etc. to the fabric surface finishing, natural fibers they use this method; the second is the IFR as a co-monomer is added to the polymer, mostly for synthetic flame.Cutting-edge research retardant nanocomposites are Cornell University and the US National Institute of Standards and Technology (NIST), they studied the nylon 6, polypropylene and polystyrene nanocomposite flame resistance, and obtained preliminary results [25]. Wang increase [26], who found that the modified montmorillonite treated add less (typically 2% to 5% by mass of the base material) dispersion, and the contact area between the maximum and the presence of additives and the polymer II chemical bond between those interfaces, so they have a perfect adhesion, can improve the thermal stability of the material does not affect the mechanical properties of the material conditions, as the basis for flame retardant system has broad application prospects.Looking 4 green flame retardantsFlame retardant is widely used for more than a halogen-containing flame retardant, although the organic halide to produce reactive halogen groups in the gas phase, can effectively change the thermal oxidation process in polymers, the use of flame retardant decomposition release of HX (e.g. HBr, HCl and HI) and the degradation of the polymer produced by the interaction of H and OH radicals that reduce the concentration of free radicals, thereby delaying or terminating burning chain reaction, but when the fire broke out, due to decomposition and combustion of these materials will produce a lot of smoke, flame and its main role played HX are toxic, corrosive gases, thereby preventing the evacuation, fire fighting apparatus and equipment corrosion and personnel, resulting in a "second disaster" and the combustion products (halide) has a long atmospheric lifetime, it is difficult to remove once into the atmosphere, polluting the atmosphere and, furthermore, it can cause damage to the ozone layer. Thus, although the halogen-containing flame retardants and is widely used to good effect, but it will still be phased out, replaced by a more clean, environmentally friendly green products.Green flame retardants such as halogen-free flame retardants, because efficient, low smoke, low toxicity and other characteristics, can eventually replace the halogen-containing flame retardants; phosphorus-based flame retardants and inorganic hydroxides should also further strengthen the research, especially in terms of flame retardants microencapsulation technology, micro technology, surface modification technology, through microencapsulation can reduce the absorption of red phosphorus hydrolysis resistance, reducing the release of toxic phosphine gas; intumescent flame retardant and polymer / inorganic nanocomposites because of its excellent flame retardant and physical properties as well as non-toxic, pollution, etc., will become the next focus of research and development. With polymer environmentally friendly flame retardant system requirements continue to increase, nano polymer / inorganic composite materials and phosphorus - nitrogen-based flame retardants, synergists should be the main directions for future research retardant modified.Green chemistry and technology will bring new industrial revolution; the future of green flame retardant industrial research should focus on the development of new and friendly low smoke, low toxicity and halogen-free products, environmentally friendly chemical reactions used in the process without poison harmless raw materials, solvents and catalysts, truly allows different media (biological, air, water and soil) have no effect or minimal impact.PreviousSome of the features on pure silk NextClassification of textile fibers

Flame retardant mechanism of polymer materials summary

The burning of the polymer is a very intense complex thermal oxidation, smoke or have to take hair blazing flame characteristics. When the combustion process is typically in the continuous heating of the external heat source, the first polymer with atmospheric oxygen free-radical chain degradation reactions produce volatile combustible material, the material reaches a certain concentration and temperature will catch fire and burn up, the combustion part of the heat evolved is supplied degradable polymer, further exacerbating their degradation, produce more combustible gas flame in a short time will spread rapidly and cause a fire.Is a class of flame retardants can prevent or inhibit flame propagation ignite plastic additives. According to its use, and the reaction can be divided into two types add type, addition type flame retardant is incorporated into the plastic during processing of the plastic, used for thermoplastics. Reactive flame retardant in the polymer synthesis process as monomers chemically bonded to the polymer chains, used for thermosetting plastics, some reactive flame retardant may be used as additive flame retardant. According to the chemical structure, can be divided into inorganic and organic flame retardant types, and more in these compounds containing a halogen and phosphorus, some contain antimony, boron, aluminum and other elements.1. Flame retardant mechanismThe flame retardant material, often by gas flame, and condensed phase flame retardant heat exchange interrupt mechanism to achieve. Inhibit the promotion of the combustion reaction chain radicals play flame retardant functions belong vapor; in the solid phase delay or prevent the polymer from the thermal decomposition of condensed phase flame retardant effect of the case; the polymer combustion section fire caused by heat away, the heat exchange mechanism are interrupted classes retardant. But combustion and flame are very complex process, involving a lot of influence and constraints, the mechanism of a flame retardant system is strictly divided into a certain kind of hard, in fact, a lot of flame retardant system simultaneously in several flame retardant mechanism works. 1.1 vapor retardant mechanismVapor retardant system refers to a gas phase combustion interrupt or delay the chain reaction of combustion flame retardant, flame under the following situations belong vapor retardant.Can produce free radical inhibitor (1) heating or combustion flame retardant material, so that the combustion chain reaction interrupted.Generating fine particles (2) when the combustion heat or flame retardant material, they can promote free radicals combined with each other to stop the combustion chain reaction.(3) the release or burn large amounts of heat-retardant materials inert gas or high-density steam, the former can be diluted oxygen and gaseous fuel, and this can reduce the temperature of the gas, resulting in the burning aborted; the latter can be covered on gas , cut it into contact with the air, thus making the combustion suffocation. Volatile, low boiling phosphorus-containing compound, such as trialkyl phosphorous oxide (R3PO), belongs to the gas phase flame retardant. Mass spectral analysis showed that the triphenyl phosphine and triphenylphosphine oxide ester cleavage fragments into free radicals in the flame, such as free radicals and a halide as capturing H O radical, thereby to restrain the combustion chain reaction effect.In the combustion and pyrolysis of red phosphorus, but also the formation of P , they and the polymer react with oxygen to generate ester structure. In addition, the expansion flame retardant system may also play a role in the gas phase, in which the amine compounds decompose when heated to produce NH3, H2O and NO, the first two can dilute the concentration of oxygen gas flame zone, which allows the combustion waging The free radical quenching, resulting in chain termination reaction.1.2 condensed phase flame retardant mechanismThis refers to the delay or interruption in the condensed phase thermal decomposition of the flame retardant material of flame retardant, flame retardant belong to the following situations are condensed phase flame retardant.(1) flame retardants phase delay or prevent combustible gas can generate heat and radical decomposition cohesion.(2) flame retardant material heat capacity larger than inorganic filler, heat storage and heat conduction through the material is not easy to achieve the thermal decomposition temperature.(3) thermal decomposition endothermic flame retardants, flame retardant materials to make the temperature rise slowed or discontinued.Generation (4) fire-retardant material on the surface of the porous carbon combustion layer that flame, heat, oxygen barrier, but also can prevent the gas into the combustion vapor, causing combustion in order to maintain continued to burn, you must have enough oxygen and combustible gas mixture. If the radicals produced by thermal cracking trapped disappear, will slow down or interrupt combustion. When the flame retardant thermoplastics flame retardant comprising an organic bromide as combustion occurs, the following reactions.RH R + H chain initiationHO + CO = CO2 + H chain growth (highly exothermic reaction)H + O2 = HO + O chain branchingO + HBr = HO - + Br chain transferHO + HBr = H2O + Br chain terminationHaving a highly reactive free radical HO play a key role in the combustion process. When HO is less reactive Br replaced terminate radical chain reaction occurs.1.3 interrupt retardant heat exchange mechanismThis means that part of the heat produced by the combustion of the flame retardant material is taken away, so that the thermal decomposition temperature of the material can not be maintained, and therefore can not be maintained to produce combustible gas, so the combustion self-extinguishing. For example, when the material is exposed to strong heat or flame combustion can melt, and the molten material is easy to drop, and thus most of the heat away, reducing the feedback to the body heat, so that the combustion delay, may eventually terminate combustion. So, flammable meltable materials are usually low, but the dripping of burning droplets can ignite other materials, increased fire risk. 2. retardant effect of a flame retardantFlame retardant effect in the combustion process is a polymer material can prevent or inhibit its physical or chemical change in speed, specifically, the role is reflected in the following aspects.(1) an endothermic effect its role is to make the temperature rise in difficulty polymeric material, e.g., borax having 10 molecules of water of crystallization, due to release of water of crystallization to seize 141.8kJ / mol of heat, leaving its endothermic rise in temperature of the material is inhibited, resulting in flame retarding effect. Flame retardant hydrated alumina is the reason for its endothermic heat dewatering effect. In addition, some of the thermoplastic polymer droplet cleavage often generated, because it can be removed leaving the combustion zone heat of reaction can also play a flame-retardant effect.(2) blocking effect and its role is to generate stable at higher temperatures the cover layer, or decomposed to generate a foam-like substance covering the surface of the polymer material, so that the heat generated by the combustion is difficult to pass the interior material, so that the polymer combustible gas generated by thermal decomposition material is difficult to escape, and the material isolated from the effects of air, thereby inhibiting the cleavage of the material, to achieve the effect of flame retardant. Such as phosphate compounds and fire foam coatings can click here to play a role in the mechanism.(3) the dilution effect of these substances decompose when heated to produce a large amount of nonflammable gas, flammable gas and oxygen in the air resulting diluted polymer material and reach the combustible concentration range, thereby preventing high polymer pyrophoric material burning. There can be used as diluent gas CO2, NH3, HCl, and H2O and the like. Will be able to produce such nonflammable gas heating amine phosphates, ammonium chloride, carbonate, amine and the like.(4) Transfer effect its role is to change the mode of thermal decomposition of the polymer material, thereby suppress the generation of the combustible gas. For example, the use of an acid or base to make the dehydration reaction to produce cellulose decomposed into carbon and water, because they do not produce a combustible gas, will not be ignited. Ammonium chloride, ammonium phosphate, phosphoric acid ester, etc. can decomposition of such materials, the catalytic material fused ring carbonization, to achieve the purpose of fire-retardant.(5) The inhibitory effect (capture free radicals), the main polymer is a free radical chain reaction of combustion, some substances can capture the combustion reaction active intermediate HO , H , O , HOO , etc, inhibit free radical chain reaction, the combustion speed is reduced until the flame is extinguished. Commonly used bromine, chlorine and other organic halogen compounds have this inhibitory effect.(6) enhancement effect (synergy) Some materials, when used alone has no effect or flame retardant effect is not, you can play a variety of materials with enhanced flame-retardant effect. Antimony trioxide and halogen compounds and use, is the most typical example. As a result, not only can improve the flame retardant efficiency, and also reduce the amount of flame retardant.Several typical flame retardant mechanism of 33.1 halogen flame retardantHalogen flame retardants include bromine-based flame retardants and chlorine. Halogen flame retardant is currently one of the world's largest production of organic flame retardants. In most of the halogen-based flame retardants are brominated flame. Industrial production of brominated flame retardants can be divided into additive, reaction type and polymer-type three categories, and variety. The domestic market of more than 20 kinds of existing additive brominated flame retardants, more than 10 kinds of polymer type brominated flame retardants, more than 20 kinds of reactive bromine-based flame retardants. Additive flame retardant mainly decaBDE (DBDPO) tetrabromobisphenol A bis (2,3 or two alkyl propyl) ether (TBAB), eight polybrominated diphenyl ethers (OBDPO) etc; reaction type flame retardants mainly tetrabromobisphenol A (TBBPA), 2, 4, 6- tribromophenol and the like; a polymer type flame retardant mainly brominated polystyrene, brominated epoxide, tetrabromobisphenol A carbonate ester oligomer and the like. Brominated flame retardants reason for being popular, mainly because of its high flame retardant efficiency, and affordable. Since the C-Br bond in the lower, most brominated flame retardants decomposition temperature at 200 -300 , this temperature range is just common polymer decomposition temperature range. Therefore, when the polymer decomposition, brominated flame retardants have begun to decompose, and captures the radical decomposition of polymer materials, thereby delaying or inhibiting the chain reaction of burning and then, while the release of HBr itself is a flame retardant gas, you can cover the surface of the material, play a role in blocking and diluted oxygen concentration. Such exceptions are all flame retardant and antimony (antimony trioxide or antimony pentoxide) compound used to make fire by synergy effect has been significantly improved.Halogen flame retardant to play a major role in the gas phase. Since hydrogen halide gas halide decomposition, is nonflammable gas, has a dilution effect. It is a larger proportion of the gas film layer covering the surface of the solid polymer materials can be isolated from the air and heat, from the mulch. More importantly, the suppression of hydrogen halide polymer chain reaction of combustion of materials, from the scavenging of free radicals. With bromide, for example, the inhibition of free radical chain reaction mechanism is as follows:Brominated flame retardants Br Br + RH R + HBrHO + HBr = H2O + Br OH radical reactions in polymer materials added brominated flame retardants, fire thermal decomposition reaction of free radicals Br , it generates polymer materials react with hydrogen bromide, hydrogen bromide and highly active On the one hand makes Br regeneration, on the one hand so that the concentration of OH radicals reduce the combustion chain reaction is inhibited, slow burning speed, until extinguished.But when the fire occurred, due to decomposition and combustion of these materials produce a lot of smoke and toxic corrosive gases cause a "second disaster" and the combustion products (halide) has a long atmospheric lifetime, once into the atmosphere is difficult to remove, seriously polluted the atmosphere, destroy the ozone layer. In addition, the combustion and pyrolysis products PBDE flame retardant polymer materials contain toxic polybrominated diphenyl and dioxane (PBDD) and polybrominated dibenzofurans (PBDF). September 1994, the US Environmental Protection Agency evaluation demonstrated that these substances on humans and animals caused by toxic substances.3.2 flame retardant mechanism of phosphorus and phosphorus compoundsPhosphorus and phosphorus compounds have long been used as a flame retardant, it was too early retardant mechanism, initially found to generate a lot of coke when using phosphorus-containing flame combustion of materials and reduce the flammability of volatile production of substance, thermogravimetric combustion retardant material is greatly reduced, but the smoke density is increased when the combustion retardant material than when no flame retardant. Based on the above facts made some flame retardant mechanism. Phosphorus compounds in different reaction zone from the role played by flame retardant mechanism can be divided into phases and vapor phase flame retardant mechanism cohesion, organophosphorus flame retardants play a role in the condensed phase, the flame retardant mechanism is as follows :When burning, non-flammable liquid phosphorus compound decomposition film-forming phosphate has a boiling point of up to 300 . Meanwhile, phosphoric further dehydration metaphosphoric acid, metaphosphoric acid and further polymerized to form poly metaphosphoric acid. In this process, not only by the phosphate coating layer covering the effects produced play, and because the resulting polyvinylidene phosphoric acid is a strong acid, is a strong dehydrating agent, dehydration and carbonization of the polymer, changing the mode of the combustion process and the polymer the formation of carbon on the surface to cut off the air, and thus play a stronger flame effect.Flame retardant phosphorus flame retardant mainly in the early stages of a fire polymer decomposition, because dehydration can promote hair polymer, thereby reducing the amount of polymer produced by thermal decomposition of combustible gas, and the resulting The carbon can cut outside air and heat. Typically, the phosphorus-based flame retardant effect of the oxygen-containing polymer of the best, which is primarily used in the hydroxyl group-containing cellulose, polyurethane, polyester and other polymers. For oxygen-hydrocarbon polymer, the phosphorus-based flame retardant effect is relatively small.Phosphorus-containing flame retardant is a free radical trapping agent, found by mass spectrometry, any phosphorus-containing compound in the polymer PO combustion has formed. It can be combined with the flame zone of the hydrogen atoms so as to suppress the flame effect. In addition, the water produced in the phosphorus-based flame retardant process, one can reduce the temperature of the condensed phase, on the other hand can dilute the concentration of combustibles in the gas phase, in order to better play a flame retardant.3.3 inorganic flame retardant mechanism ofInorganic flame retardants include aluminum hydroxide, magnesium hydroxide, graphite, borate, oxalate, aluminum, and zinc sulfide-based flame retardant. Aluminum hydroxide and magnesium hydroxide is a flame retardant inorganic main varieties, it has no toxicity and low smoke and so they absorb heat due to thermal decomposition of the burning zone, the temperature of the combustion zone is reduced to below the critical temperature of the combustion burner self-extinguishing : After the decomposition of metal oxides most high melting point, good thermal stability, covering the surface of the solid phase in the burning heat conduction and thermal radiation barrier, which play a role in flame. At the same time generate a lot of water vapor decomposition, can be diluted combustible gases, but also play a flame retardant.Alumina hydrate has good thermal stability, heated at 300 2h may be converted to AlO (OH), does not produce harmful gases upon contact with the flame, and to neutralize released acid gas is pyrolysed polymer, hair smoke less, cheap, etc., so it becomes important species of inorganic flame retardants. Hydrated alumina combined heat released from the chemical water absorbs the heat of combustion, reducing combustion temperature. When play a flame retardant, mainly two crystal water works, in addition, activated alumina dehydration product, some of the polymer can promote the fused ring charring during combustion, thus having a condensed phase flame retardant. This mechanism is known from the use of hydrated alumina as a flame retardant additive amount should be bigger.Magnesium main varieties of magnesium hydroxide flame retardant, a flame retardant is being developed at home and abroad in recent years, it starts at about 340 endothermic decomposition reaction of magnesium oxide, the weight loss at 423 reached its maximum , the decomposition reaction at 490 terminated. From calorimetry, it appears that the reaction to absorb a lot of heat (44.8KJ / mol), the resulting water also absorbs a lot of heat, reducing the temperature to reach the flame retardant. Thermal stability and smoke suppression capacity than the hydrated alumina magnesium hydroxide good, but because of the large surface polarity of magnesium hydroxide, poor compatibility with an organic substance, it is necessary after surface treatment can be used as effective flame retardants. In addition, its thermal decomposition temperature is high, the decomposition of suitable thermoset materials of relatively high temperature polymer flame retardant.At high temperature, heat expandable graphite intercalation layer easily degradable, so that the generated gas of the graphite layer spacingQuickly expanded to several times its original to several hundred times. When expandable graphite is mixed with the polymer, the flame may beUse under tough carbon layer can be generated in the polymer surface, which play a role in flame.Borate flame retardants borax, boric acid and zinc borate. At present, the main use of zinc borate. Zinc borate300 crystals began to release water, under the action of a halogen compound, to generate a boron halide, zinc halide, inhibit and capture free hydroxyl, preventing combustion chain reaction; while forming a solid phase covering layer, isolated from ambient oxygen, prevent flame continues to burn and has a smoke suppression effect. Zinc borate can be used alone, can also be used with other flame retardant compound. At present, the main products are fine zinc borate, zinc borate heat, anhydrous zinc borate and zinc borate high water.Aluminum oxalate is a crystalline substance derived aluminum hydroxide, low alkali content. When the polymer contains oxalic acid aluminum combustion, releasing H20, CO and CO2, without generating corrosive gas, aluminum oxalate also reduce cigarette smoke density and speed. Since aluminum oxalate of low alkali content, so when using the flame-retardant wire, cable coating materials, do not affect the electrical properties of the material.Now developed five kinds of zinc sulfide-based flame retardant, wherein the four kinds used in rigid PVC, another may be used in soft PVC, polyolefins diameter and nylon. Such flame retardants can improve the anti-aging properties of the material, and there is good compatibility and enhance the thermal stability of polyolefins and fiberglass.3.4 synergistic flame retardant mechanism of mixed useHalogen-containing flame retardants used in conjunction with the phosphorus can generate significant synergies. For halogen - phosphorus flame retardant synergistic effect has been proposed halogen - phosphorus used in conjunction with each other to promote decomposition and the formation of a stronger than the single use of halogen flame retardant effect - phosphorus compounds and their conversion products PBr3, PBr , POBr3 so on. By pyrolysis gas chromatography, differential thermal analysis, differential scanning calorimetry analysis, oxygen index, the researchers observed flame temperature programmed methods such as halogen-phosphorus showed a synergistic effect, halogen - phosphorus flame retardants used in conjunction with decomposition slightly lower temperature than when used alone, and the decomposition is very intense, smoke clouds of chlorine and phosphorus compounds combustion zone formed hydrolyzate can stay a long time in the combustion zone to create a strong vapor barrier.About P - N interaction mechanism was not perfect, is generally believed by nitride (such as urine, melamine, guanidine, dicyandiamide, methylolmelamine etc.) can promote cellulose phosphate and phosphorylation reactions. Amine phosphates formed more easily occurs as the cellulose ester, the thermal stability of such esters thermal stability than phosphate. Phosphorus - nitrogen flame retardant system can promote the formation of coke and water sugars decompose at lower temperatures, and increased production of coke residue, thereby enhancing the flame retarding effect. Phosphide and nitride formation expandable coke layer at a high temperature, it acts as an oxygen barrier protective insulating layer, a nitrogen-containing compound acts as a blowing agent and a char enhancer. Basic element analysis showed that the residue of nitrogen, phosphorus, oxygen three elements, the thermal stability of the amorphous substance which is formed at the flame temperature, like glass body, as an insulating protective layer of cellulose.Can not be used alone as a flame retardant antimony trioxide (except halogen-containing polymer), but with a halogen-based flame retardant is greatly enhanced synergistic effect. This is because the presence of halides in the case of antimony trioxide, the relative density of the combustion generated SbCl3, SbBr3 antimony halide such as large, since the polymer covering the surface of the covering effect, and also when the gaseous capture free radicals effect. For example, antimony trioxide and chlorinated flame retardants and use, due to thermal decomposition of hydrogen chloride chloride, hydrogen chloride and antimony trioxide reacts antimony trichloride and chlorine oxide, antimony oxide, antimony thermal decomposition of chlorine continues to generate trichlorosilane antimony.Hydrated zinc borate and halogenated flame retardants used in conjunction with good synergy. Under combustion conditions, and the cleavage products between them by the interaction, allows almost all elements can exert flame retardant effect. Hydrated zinc borate reaction product with a halogen-based flame retardant and zinc dihalide boron trihalides, they can capture HO in the gas phase, H , in the solid phase to form a glassy insulating layer, heat, oxygen barrier, water generated dilute oxygen combustion zone and take away the heat of reaction, and therefore can play a larger role in flame.Retardant mechanism 3.5 expansion systemIntumescent flame retardant system main components can be divided into three parts acid source, carbon source, gas source. Acid source is generally heated to an inorganic acid or an inorganic acid generating compound 100 ^ -250 , such as phosphoric acid, sulfuric acid, boric acid, various ammonium salts, phosphates, and borates; carbon (char-forming agent) is forming a base layer of carbonized foam, generally polyhydroxy compound is carbon-rich, such as starch, pentaerythritol and its dimers, trimers and organic resin including a light group; gas source (foam source) or more for an amine amides, such as melamine, dicyandiamide, amine polyphosphate.

Intumescent systems char complicated structure, many factors. Chemical structure and physical properties of the polymer body, the expansion flame retardant composition, conditions (such as temperature and oxygen content) during combustion and pyrolysis, the crosslinking reaction rate, and many other factors have an impact on the expansion of the structure of the char. The protective effect of the thermal expansion of the carbon layer depends not only on the coke yield, char layer height, char layer structure, the thermal stability of the protective char layer, and also depends on the chemical structure of the carbon layer, especially the emergence of a cyclic structure increases the thermal stability resistance, in addition to the chemical bond strength, and the number of crosslinks.Intumescent systems generally considered flame retardant mechanism for condensed phase flame retardant, amine polyphosphate first thermal decomposition, generate a strong dehydration of the phosphoric acid and pyrophosphoric acid, pentaerythritol ester, and then dehydrated carbonized, and the water vapor formed by the decomposition reaction of melamine Ammonia make charcoal layer expands, eventually forming an extra layer of microporous carbon layer, so isolated from the air and heat transfer, protective polymer body, to fire purposes.Intumescent flame retardant added to the polymer material, you must have the following properties: good thermal stability, can withstand high temperature polymer processing of more than 200 ; thermal degradation due to large amounts of volatile substances to be released, and the formation of residues, and the procedure should not adversely affect the expansion of the foaming process; such flame-retardants have uniform distribution in the polymer, during the combustion of materials can form a layer completely covering the surface of the expanded carbonaceous material; flame retardants must be retardant polymers have good compatibility, adverse effects can occur with polymers and additives, not too much deterioration in the physical and mechanical properties of the material. Intumescent flame retardant than the general non-halogen flame retardants is that no antimony oxide: smoke, less toxic, non-corrosive gases; expansion of flame-generated carbon layer can absorb fire melted polymer to prevent Its dripping spread fire.3.6 ammonium retardant mechanismAmmonium poor thermal stability, release ammonia when heated, such as [NH4) 2SO4, which decomposition process is as follows:[NH4) 2SO4 NH4HSO4NH4HSO4 H2SO4 ten NH3 Ammonia released difficult nonflammable gas, which dilutes the oxygen in the air; H2SO4 formation plays dehydration charring catalyst. The latter effect is generally considered a major additional experiments show, NH3 also occur following reaction in the fire:NH3 + O2 N2 + H2OAnd with deep oxidation products, such as N2O4, which can be seen not only physical NH3 retardant effect, but also the chemical flame retardant.3.7 nanocomposite flame retardant material mechanismNanocomposites singled out, although both belong to the complex fire, but the principle little different. Nanocomposite material refers to one or more components to nanometer size or molecular dispersed in another component of the matrix, this study only 10 years of history. Experiments show that the nano material with ultra-fine size exist, so the performance of various types of nanocomposites are greatly improved than the corresponding macro or micro-scale composite materials, wherein the thermal stability and flame retardant properties of the material will be improved greatly.Some scaly inorganic able fragmentation in the role of the physical and chemical structure of a nano-sized micro-district,Its lamellar spacing typically a few tenths to a few nanometers, they only allow certain polymer intercalated into the nanoInterlayer space size to form "intercalated nanocomposite", and, an inorganic interlayer will be a large aspect ratio of the polymer formed softened inorganic single sheet, uniformly dispersed in the matrix polymer, the formation of "delamination nanocomposites." The use of a porous or layered inorganic compound properties, preparation of inorganic / polymer nanocomposite, in the process of thermal decomposition and combustion, carbon and inorganic salts may be formed multi-layer structure, heat insulation and prevent the combustible gases to effect, retardant polymers to make. In addition, the use of inorganic / polymer nanocomposites also has anti-corrosion, anti-leakage, wear and weathering effect. Now nanocomposite nylon / clay, PS / clay nanocomposites, PET / clay nanocomposites, PBT / clay nanocomposites, research PP / clay nanocomposites such as nanocomposites made gratifying achievements.3.8 silicone flame retardantsThe silicone compounds as flame retardants research began in the early 1980s. In 1981, Kamber and other published studies on methyl silicone blend of polycarbonate and polyethylene, can improve the flame retardancy. Although silicone flame behind the research and development department and phosphorus flame retardant halogen, however, silicone flame retardants as a new class of non-halogenated flame retardants, with its excellent flame resistance, moldability and environment-friendly and unique style. Silicone flame retardant silicone oil, silicone resin, polysiloxane with functional groups, a polycarbonate siloxane copolymer silicone acrylate composite material and a silicone gel and the like. A silicone compound flame retardant polymer materials, silicone flame will probably migrate to the surface of the material to form a surface layer of silicone polymer concentration gradient materials.Once burned, it will generate a unique silicone-containing inorganic thermal insulation for a S iO button and a Si-C- bonds, both to prevent the combustion decomposed into material to escape, but also inhibits the polymer material thermal decomposition, reaching a high flame-retardant, low smoke, low harmful purposes. At present, the development and application of silicone flame retardants American DowCorning developed and commercialized "DC RM" series flame retardants: Japan's NEC and GE Toshiba Silicones joint research and development of silicone flame "XC-99-B6645 "; also developed SFR104 American GE silicone resin.(End)Supplementary information:An intumescent flame retardant compositionIFR is mainly composed of three parts: charring agent (carbon source), charring catalyst (acid source), expanders (air). Charring agent for the expansion of the porous carbon layer of carbon source, usually carbon-rich multi-functional groups (eg -OH) material, pentaerythritol (PER) and two acetal, three acetal is commonly charring agent. Charring catalyst is generally releasable inorganic acid compound under heating. Inorganic acids require high boiling point, but not too strong oxidizing. Ammonium polyphosphate (APP) is commonly used charring catalyst. Bulking agent is an inert gas heated release compound, generally ammonium and amides substances, such as urea, melamine, dicyandiamide and derivatives thereof. The criteria for selecting the components as follows:1) acid source: In order to have a practical, acid source must be able to make the carbonaceous polyol dehydration. Before the fire, we do not want the dehydration reaction, so commonly used acid source is a salt or ester. Acid source acid must be released at a lower temperature, in particular below the decomposition temperature of the polyol. If the organic fraction contribute to carbon, organic phosphide better.2) carbon source: the number of carbon sources and carbon content and the effectiveness of active hydroxyl groups concerned. Carbon source should be at a lower temperature by itself or matrix decomposition of the catalyst prior to the reaction.3) gas source: the blowing agent must be at the appropriate temperature decomposed, and release large amounts of gas. Foam should be melted before solidification occurs. Appropriate temperature and system-related. For a particular intumescent flame retardant polymer system, do not need the three components are present simultaneously, the polymer itself can sometimes serve as an element therein. Using the above criteria can predict the effectiveness of most of the system.2 flame retardant mechanismWhen the intumescent flame retardant heat, charring agent in the charring catalyst dehydration into carbon, carbides under the effect of the expansion agent gas decomposition char layer formed fluffy closed pore structure. Once formed, its own non-combustible, and can weaken the heat conduction between the polymer and the heat source, and prevent gas diffusion. Once combustion can not get enough fuel and oxygen combustionThe polymer will be self-extinguishing. This char layer formation through the following steps.(1) can be released at a lower temperature esterified polyhydric alcohols can be used as a dehydrating agent is an inorganic acid from the acid source.(2) at a temperature slightly higher than the release of an acid, esterification, and the system can be used as an amine esterification catalyst.(3) System melted before the esterification or the esterification process.(4) generated by the reaction of water vapor and non-combustible gases generated by the gas supply system expansion molten foam.(5) reaction nears completion, the system gelled and cured, the final form of the porous carbon foam layer. On the basis of the above discussion, it seems any of several compounds containing functional groups can be foam, foam albeit to varying degrees, in fact, this is wrong. For foaming, each reaction must occur almost simultaneously, but must be carried out in strict order. Intumescent flame retardant may also have a role in the gas phase, because phosphorus - nitrogen - carbon system when exposed to heat may produce NO and NH3, and they combine to make a radical chain reaction resulting in combustion terminated.Factors affecting intumescent flame retardant effectIntumescent flame retardant effect depends char reaction, swelling reactions and carbon layer structure.3.1 char reactionChar intumescent flame retardant effect was mainly due to thermal decomposition of the acid source APP phosphate and pyrophosphate strong dehydration, which generate phosphate dehydration and charring agent hydroxyl or amino or deamination reaction. The combustion heat generated by the decomposition of an ester of unsaturated olefins, then the carbon layer multi-molecular cyclization polymerization reaction to form a stable polyaromatic structures unsaturated olefin occurs, instead of the aromatic structure in the branched alkyl group is a small molecule is broken .Char reaction common APP and PER system in several steps in the process. First, APP long strand phosphorothioate linkages generated when 210 . After dehydration and ammonia, can form the cyclic phosphate. If the temperature continues to rise, by carbonization reaction, phosphate bond is almost completely broken, an unsaturated carbon-rich structures, reactions may have Diels-Aider reaction, making the cyclic olefins, aromatics and thick hydrocarbon structure into the coke structure.3.2 expansion reactionExpansion is due to gas migration caused cleavage. Migration rate and viscosity of the melt and the combustion zone related to the amount of gas emitted, by controlling the viscosity of the polymer can influence the degree of crosslinking and thus to adjust the carbon structure. Expansion of the carbon layer shape enclosed chamber will depend on the number and the viscosity of the gas released into the matter when carbon char. Expanders must meet the gas release process and carbonization process match. Decomposition temperature of the foaming source is too low, the gas into carbon before the spill, would not achieve the foaming action; foam decomposition temperature is too high, the gas may be carbon layers from the top or blow away. Urea is not a good match and APP-PER system. Though urea can release 70% of the gas, but its decomposition temperature (150 ~ 230 ) and expandable layer (APP- PER) formation temperature (280 ~ 320 ) compared to low. Melamine can occur in a range of 250 ~ 380 reaction, gas evolution, as commonly used bulking agents. In addition, PER PER ether phosphoric acid ester structure and the structure of the carbonization reaction will occur upon heating swelling phenomenon.3.3 carbon layer structureExpansion of the system by the carbon polymer incomplete cleavage or oxidation at a lower temperature. The rate of formation of carbon quickly and relates to thermal oxidation. Char formation of complex structures such as barrier decomposition gases and molten polymer through the barrier. Expansion of multiple carbon layers, expansion rate, strength and composition of the carbon layer is an important factor affecting the quality. According to another report, a number of physical properties of the carbon layer, such as penetrating geometric swelling degree of mechanical strength, continuity, the opening and closing of the hole, the more efficient gas and liquid. SEM is displayed after adding inorganic additives, carbon honeycomb structure tends to crack, so that the oxygen index fell. In order to ensure a good flame retardancy, the size of the chamber should be controlled in a certain range. This is because although the air chamber can lower the thermal conductivity, but if the cell size is too large, the air convection can improve the thermal conductivity. Thermal conductivity increases cause thermal degradation accelerate, thereby reducing flame retardant.