CN105924645A - Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant - Google Patents

Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant Download PDF

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CN105924645A
CN105924645A CN201610367266.9A CN201610367266A CN105924645A CN 105924645 A CN105924645 A CN 105924645A CN 201610367266 A CN201610367266 A CN 201610367266A CN 105924645 A CN105924645 A CN 105924645A
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fire retardant
diamidogen
halogen
flame retardant
phenyl ring
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罗振扬
赵昱贺
吴爽
万元俊
沈晟光
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Nanjing Forestry University
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Nanjing Forestry University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644Poly(1,3,5)triazines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065Preparatory processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition

Abstract

The invention discloses a halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and a preparation method of the halogen-free expanding flame retardant. According to the flame retardant, benzodiazepines diamine is introduced, the thermal stability of products is improved, the charring forming amount is increased, and the flame retardant is directly applied to various thermoplastic and thermosetting materials without the synergistic effect of an APP. Meanwhile, each single triazine ring contains 1-oxy-phospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octyl group, is high in contents of phosphorus and hydroxyl, and can serve as a reactive and expanding flame retardant. The flame retardant belongs to a polymerization reaction product formed by substituting 1-oxy-phospha-4-hydroxymethyl-2,6,7-trioxabicyclo[2.2.2]octane and benzodiazepines diamine with cyanuric chloride and connecting the triazine rings with one another.

Description

A kind of containing polymerization macro molecular triazine ring halogen-free expansion fire retardant and preparation method
Technical field
The present invention relates to a kind of fire retardant and preparation method, more specifically to one containing polymerization macro molecular triazine ring halogen-free expandable Type fire retardant and preparation method.
Background technology
Fire retardant in early days is mainly based on halogen flame, and halogen flame is because its consumption is few, flame retarding efficiency is high and wide adaptability Etc. advantage, capture most of polymer flame retardant market.But the shortcoming of halogen flame is to generate substantial amounts of cigarette during burning With poisonous and have corrosive gas, big to environment and harm, therefore the most a lot of fields limit halogen flame Application.
Using expansion type flame retardant in the polymeric material is study hotspot in recent years.G.Camino et al. (Camino, G. Martinasso,C.Costal,L.Thermal degradation of pentaerythritol diphosphate,model compound for fire retardant intumescent systems:PartⅠ-Overall thermal degradation.Polymer Degradation Stability, 1990,27 (3): 285~296) research to expanded flame-retardant polypropylene, open one for the development of flame retardance of polymer technology New approach.Expansion type flame-retardant polymer has high flame retardant, without molten drop behavior, long-time or repeated exposure are had in flame Fabulous repellence;Halogen, non-oxidation antimony;The advantages such as low cigarette, low toxicity, non-corrosiveness gas.Therefore flame-retarded technology it is described as Revolution.Expansion type flame retardant (Intumescent Flame Retardant, IFR) is a kind of novel halogen-free flame retardants, Because its gas harmless of release, neat coal amout layer of charcoal that is big and that generate when burning can be effectively prevented the advantages such as polymer molten drop, It is particularly well-suited to the fire-retardant of polymer.So, expansion type flame retardant flame retardant area at home and abroad increasingly comes into one's own.Intumescent Fire retardant systems mainly contains acid source, carbon source and source of the gas three class component.In traditional expansion type flame retardant system, much more general with APP (APP), polyhydric alcohol and Cyanuric Chloride compounding ingredients composition, therefore, generally believe that the fire retardant mechanism of intumescent system is: APP decomposes, generates phosphoric acid and the pyrophosphoric acid with strong dehydration, makes tetramethylolmethane (PER) be esterified, and then Dehydration carbonization.Steam and the ammonia of triazine ring decomposition that reaction is formed make layer of charcoal expand, and ultimately form one layer of microporous carbon-coating, Thus completely cut off air and heat transfer, protect polymer body, reach fire-retardant purpose.Theoretically, the formation master of foamed char Experience following step: under (l) lower temperature (about 150 DEG C), acid source releasing can esterification polyol and can be as dehydrant Mineral acid;(2) at slightly higher temperature, mineral acid and polyhydric alcohol (carbon source) carry out esterification, and the amine in system is then as esterification The catalyst of reaction, makes esterification acceleration;(3) system melts before esterification or in esterification;(4) course of reaction The water vapour of middle generation and produced non-flammable gases by source of the gas and make the system being in molten condition expanded foamed.Meanwhile, many Unit's alcohol and ester dehydration carbonization, form inorganic matter and charcoal residue, and system be the most expanded foamed;(5) when reaction is nearly completed, System gel and solidification, eventually form porous foam layer of charcoal.
When thermal polymer degradation generates the high cross-linked structure of heat stability or aromatic rings, neat coal amout will increase.In combustion, Become charcoal that the anti-flammability of polymer is had the biggest impact.Therefore, develop efficient carbon forming agent, particularly can promote polymerization Thing self more participates in into the expansion type flame retardant of charcoal, is significant.Triazine system derivant is that a big class is rich in tertiary carbon The compound of structure, has excellent charred effect.At different temperatures, reactivity is or not three chlorine atoms in Cyanuric Chloride With.Utilize this feature of Cyanuric Chloride, can be designed that different hydroxyl, P elements etc. various structures carbon forming agent or Integrate the haplotype expansion type flame retardant of source of the gas, carbon source, acid source.Nitrogen-containing compound based on pyrrolotriazine derivatives is as IFR Novel carbon forming agent in system, it has proved that the fire retardation improving IFR is had significant cooperative effect.Triazine system derivant It is mainly characterized by from its starting material Cyanuric Chloride, and reacts containing the most isoplastic compound, can synthesize multiple chemical combination Thing, it mainly has the advantage that (1) Halogen, low toxicity;(2) decomposition temperature is high;(3) physical and mechanical properties of material is affected little; (4) exudation;(5) flame retarding efficiency is high.
Xuejun Lai et al. (Lai X J, Tang S, Li H Q, et al.Flame-retardant mechanism of a novel polymeric intumescent flame retardant containing caged bicyclic phosphate for polypropylene[J]. Polymer Degradation and Stability, 2015,113,22-31.) utilize 1-epoxide phospha-4-methylol-2,6,7-trioxa double Ring [2.2.2] octane (PEPA) and Cyanuric Chloride one replacement, then generate macromole expansion type flame retardant with ethylenediamine polyreaction PETBP, introduces phosphorus into triazine ring, adds the flame-retardant expanded effect of triazine ring.The PEPA introduced is cage cyclic phosphorus-containing chemical combination Thing, improves the heat stability of triazine ring, adds its oxygen content, fire-retardant during acid source, source of the gas sufficient, flame retardant effect obtains Arrive raising.If again phenyl ring class diamidogen being introduced and making triazine ring be connected and synthetic macromolecule expansion type flame retardant.Compared to In PETBP, ethylenediamine is as the polymeric chain between triazine ring, introduces the diamidogen of phenyl ring class, improves the heat stability of product, Add its neat coal amout, it is not necessary to the synergism of APP and be used directly in various thermoplasticity, thermosets, application Prospect is the most wide.
Summary of the invention
It is an object of the invention to provide a kind of containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, this fire retardant introduces benzene The diamidogen of ring class, improves the heat stability of product, adds its neat coal amout, it is not necessary to the synergism of APP and be directly used in In various thermoplasticity, thermosets.The most each triazine monocycle is double containing all there being 1-epoxide phospha-4-methylol-2,6,7-trioxa Ring [2.2.2] octyl group, phosphorous, amount of hydroxyl groups is high, can do response type expansion type flame retardant.
The present invention also provides for this preparation method containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, mainly by three polychlorostyrene Cyanogen and 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] octane, phenyl class diamidogen react, and preparation method is simple Easy.
Technical scheme is as follows:
The present invention containing polymerization macro molecular triazine ring halogen-free expansion fire retardant be Cyanuric Chloride respectively with 1-epoxide phospha-4-methylol -2,6,7-trioxa-l-phosphabicyclo [2.2.2] octane one replacements, phenyl class diamidogen one replacement, and make triazine ring be connected polymeric reaction product.
The present invention is above-mentioned containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, and its further technical scheme is described phenyl ring Class diamidogen is p-phenylenediamine, p dimethylamine, 2,4 di amino toluene, 2,6-diaminotoluene, 4,4'-benzidine or 4,4'- MDA.
The present invention is above-mentioned containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, and its further technical scheme is described benzene When ring class diamidogen is p-phenylenediamine, fire retardant concrete structure formula is:
When described phenyl ring class diamidogen is p dimethylamine, fire retardant concrete structure formula is:
When described phenyl ring class diamidogen is 2,4 di amino toluene, fire retardant concrete structure formula is:
Described phenyl ring class diamidogen is 2, and during 6-diaminotoluene, fire retardant concrete structure formula is:
Described phenyl ring class diamidogen is 4, and during 4'-benzidine, fire retardant concrete structure formula is:
Described phenyl ring class diamidogen is 4, and during 4'-MDA, fire retardant concrete structure formula is:
The present invention is above-mentioned contains the preparation method being polymerized macro molecular triazine ring halogen-free expansion fire retardant, and it comprises the following steps:
1) add Cyanuric Chloride and solvent, stirring in a kettle., make Cyanuric Chloride dispersed, control to drip at-5 DEG C~5 DEG C Add and drip 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] octane and acid binding agent so that solution ph is 5~8, Reacting 3~4 hours after being added dropwise to complete, pH stable is 7~8, and reaction separates after terminating, and obtains intermediate product one;
2) temperature is increased to 40 DEG C~55 DEG C, stirring so that intermediate product one uniform distribution in a solvent, continues to control dropping benzene Ring class diamidogen and acid binding agent so that pH value is 5~8, react 6~8 hours after being added dropwise to complete, pH stable is 7~8, instead Should separate after terminating, obtain intermediate product two;
3) temperature is increased to 95 DEG C~105 DEG C, stirring so that intermediate product two uniform distribution in a solvent, continues to control dropping Phenyl ring class diamidogen and acid binding agent so that pH value is 5~8, react 10~12 hours after being added dropwise to complete, pH stable 7~8, Reaction separates after terminating, and obtains containing polymerization macro molecular triazine ring halogen-free expansion fire retardant.
The preparation method that the present invention is above-mentioned, its further technical scheme be described acid binding agent be sodium bicarbonate, sodium carbonate, hydrogen Sodium oxide, potassium hydroxide, triethylamine, pyridine, triethylene diamine, N-methylmorpholine, tetramethylethylenediamine, 1,8-diaza two Ring 11 carbon-7-alkene or DMAP.Described acid binding agent is preferably sodium bicarbonate or triethylamine.
The preparation method that the present invention is above-mentioned, its further technical scheme can also is that described phenyl ring class diamidogen be p-phenylenediamine, P dimethylamine, 2,4 di amino toluene, 2,6-diaminotoluene, 4,4'-benzidine or 4,4'-MDA.
The preparation method that the present invention is above-mentioned, its further technical scheme can also is that step 1) and step 2) described in solvent Volume ratio for acetone and the mixture of water, acetone and water is 1:1~1.5.
The preparation method that the present invention is above-mentioned, its further technical scheme can also is that step 3) described in solvent be toluene.
Compared with prior art beneficial effects of the present invention is as follows:
The fire retardant that the present invention obtains adds to can prepare the polymer with fire resistance in polymer.The present invention is to use Flame-retardant polymer prepared by the inventive method is not particularly limited.Can formula, physical mixed routinely.Hereby it is applicable to each Plant thermoplastic polymer such as polypropylene, polyethylene, polrvinyl chloride, polystyrene, polymethyl methacrylate, polyamide, gather Carbonic ester, poly-terephthalate analog thermoplastic polyester etc.;Can also be used for various thermosetting resin, such as epoxy resin, polyurethane etc. In do firming agent or auxiliary agent and use.
Fire retardant synthesized by the present invention adds 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] octyl group so that resistance What in combustion agent, carbon-coating was formed is finer and close, improves flame retardant effect;Add phosphorus series elements, mainly play fire retardation at condensed phase, Especially to oxygen-containing polymers material.Compared to ethylenediamine in PETBP as the polymeric chain between triazine ring, also introduce phenyl ring The diamidogen of class, improves the heat stability of product, adds its neat coal amout, it is not necessary to the synergism of APP and be directly used in each Plant in thermoplasticity, thermosets.
In the preparation method of the present invention, synthetic reaction process is continuous, and synthesis technique is simple, and generated time is it is generally required to 15 to 25 Hour.The method can design different rate of charge according to the requirement participating in polymer, thus can get the macromole of different molecular weight Chain..
Detailed description of the invention
Embodiment 1
The three of 18.45g are added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer Polychlorostyrene cyanogen and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed, so After under conditions of 0 DEG C, be the most uniformly slowly added dropwise 18g 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] Octane and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), after dropping, under conditions of 0 DEG C React 3 hours.Then liter high-temperature is to 40 DEG C, adds 100ml acetone soln, is more uniformly slowly added dropwise 5.4g in reaction bulb P-phenylenediamine and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), keep temperature 40 DEG C, drip complete After, then react 8 hours under the conditions of this.Then sucking filtration wash to obtain second step product with water, puts it into 1L there-necked flask In, add 300ml toluene, then heat to 95 DEG C, in reaction bulb, be uniformly slowly added dropwise 5.4g p-phenylenediamine and triethylamine Toluene solution (10.4g triethylamine is dissolved in 100ml toluene), is stirred at reflux reaction 10~12 hours, and reaction will be produced after terminating Thing steams drying, again with toluene washing, sucking filtration, then filtrate is steamed drying, obtains containing polymerization macro molecular triazine ring halogen-free expandable Type fire retardant (I), productivity is 83.2%.Its structural formula is:
When macro molecular triazine ring halogen-free expansion fire retardant (I) is blended with polypropylene 1:4, its limited oxygen index (LOI) after measured Being 43.19%, UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 2
The three of 18.45g are added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer Polychlorostyrene cyanogen and 100ml acetone soln (volume ratio of acetone and water is 1:1.5), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed, Then, under conditions of-5 DEG C, 18g 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos the most uniformly it are slowly added dropwise [2.2.2] octane and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), after dropping, at-5 DEG C Under the conditions of react 4 hours.Then liter high-temperature is to 50 DEG C, adds 100ml acetone soln, more slowly drips in reaction bulb Add 6.8g p dimethylamine and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), keep temperature 50 C, After dropping, then react 6 hours under the conditions of this.Then sucking filtration wash to obtain second step product with water, puts it into 1L In there-necked flask, add 300ml toluene, then heat to 98 DEG C, in reaction bulb, be uniformly slowly added dropwise 6.8g p dimethylamine With the toluene solution (10.4g triethylamine is dissolved in 100ml toluene) of triethylamine, it is stirred at reflux reaction 11~12 hours, reaction After end, product is steamed drying, the washing of again with toluene solution, sucking filtration, then filtrate is steamed drying, obtain containing polymerization macromole Triazine ring halogen-free expansion fire retardant (II), productivity is 89.14%.Its structural formula is:
When macro molecular triazine ring halogen-free expansion fire retardant (II) is blended with polypropylene 1:4, its limited oxygen index (LOI) after measured Being 37.01%, UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 3
The three of 18.45g are added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer Polychlorostyrene cyanogen and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed, so After under conditions of 5 DEG C, be the most uniformly slowly added dropwise 18g 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] Octane and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), after dropping, under conditions of 5 DEG C React 3 hours.Then liter high-temperature is to 45 DEG C, adds 100ml acetone soln, is more uniformly slowly added dropwise 6.15g in reaction bulb 2,4 di amino toluene and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), keep temperature 45 C, drip After adding, then react 7 hours under the conditions of this.Then sucking filtration wash to obtain second step product with water, puts it into 1L In there-necked flask, add 300ml toluene, then heat to 105 DEG C, in reaction bulb, be uniformly slowly added dropwise 6.15g 2,4-diamino The toluene solution (10.4g triethylamine is dissolved in 100ml toluene) of base toluene and triethylamine, is stirred at reflux reaction 11~12 hours, Product is steamed drying after terminating by reaction, and again with toluene solution washs, sucking filtration, then filtrate is steamed drying, obtains containing polymerization big Molecule triazine ring halogen-free expansion fire retardant (III), productivity is 81.55%.Its structural formula is:
When macro molecular triazine ring halogen-free expansion fire retardant (III) is blended with polypropylene 1:4, its limited oxygen index (LOI) after measured Being 42.35%, UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 4
The three of 18.45g are added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer Polychlorostyrene cyanogen and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed, so After under conditions of 5 DEG C, be the most uniformly slowly added dropwise 18g 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] Octane and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), after dropping, under conditions of 5 DEG C React 3 hours.Then liter high-temperature is to 50 DEG C, adds 100ml acetone soln, is more uniformly slowly added dropwise 6.15g in reaction bulb 2,6-diaminotoluene and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), keep temperature 50 C, drip After adding, then react 7 hours under the conditions of this.Then sucking filtration wash to obtain second step product with water, puts it into 1L In there-necked flask, add 300ml toluene, then heat to 100 DEG C, in reaction bulb, be uniformly slowly added dropwise 6.15g 2,6-diamino The toluene solution (10.4g triethylamine is dissolved in 100ml toluene) of base toluene and triethylamine, is stirred at reflux reaction 11~12 hours, Product is steamed drying after terminating by reaction, and again with toluene solution washs, sucking filtration, then filtrate is steamed drying, obtains containing polymerization big Molecule triazine ring halogen-free expansion fire retardant (IV), productivity is 87.08%.Its structural formula is:
When macro molecular triazine ring halogen-free expansion fire retardant (IV) is blended with polypropylene 1:4, its limited oxygen index (LOI) after measured Being 45.64%, UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 5
The three of 18.45g are added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer Polychlorostyrene cyanogen and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed, so After under conditions of 5 DEG C, be the most uniformly slowly added dropwise 18g 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] Octane and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), after dropping, under conditions of 5 DEG C React 3 hours.Then liter high-temperature is to 50 DEG C, adds 100ml acetone soln, is more uniformly slowly added dropwise 9.3g in reaction bulb 4,4'-benzidine and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), keep temperature 50 C, drip After adding, then react 7 hours under the conditions of this.Then sucking filtration wash to obtain second step product with water, puts it into 1L In there-necked flask, add 300ml toluene, then heat to 100~105 DEG C, in reaction bulb, be uniformly slowly added dropwise 9.3g 4,4'- The toluene solution (10.4g triethylamine is dissolved in 100ml toluene) of benzidine and triethylamine, is stirred at reflux reaction 11~12 Hour, product is steamed drying after terminating by reaction, and again with toluene solution washs, sucking filtration, then filtrate is steamed drying, is contained Polymerization macro molecular triazine ring halogen-free expansion fire retardant (V), productivity is 84.27%.Its structural formula is:
When macro molecular triazine ring halogen-free expansion fire retardant (V) is blended with polypropylene 1:4, its limited oxygen index (LOI) after measured Being 43.29%, UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 6
The three of 18.45g are added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer Polychlorostyrene cyanogen and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed, so After under conditions of 5 DEG C, be the most uniformly slowly added dropwise 18g 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] Octane and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), after dropping, under conditions of 5 DEG C React 3 hours.Then liter high-temperature is to 50 DEG C, adds 100ml acetone soln, is more uniformly slowly added dropwise 10g 4,4'-in reaction bulb MDA and NaHCO3Solution (8.4g NaHCO3It is dissolved in 100ml distilled water), keep temperature 50 C, drip After adding, then react 7 hours under the conditions of this.Then sucking filtration wash to obtain second step product with water, puts it into 1L In there-necked flask, add 300ml toluene, then heat to 95~105 DEG C, in reaction bulb, be uniformly slowly added dropwise 10g 4,4'-bis- The toluene solution (10.4g triethylamine is dissolved in 100ml toluene) of diaminodiphenylmethane and triethylamine, is stirred at reflux reaction 11~12 Hour, product is steamed drying after terminating by reaction, and again with toluene solution washs, sucking filtration, then filtrate is steamed drying, is contained Polymerization macro molecular triazine ring halogen-free expansion fire retardant (VI), productivity is 90.19%.Its structural formula is:
When macro molecular triazine ring halogen-free expansion fire retardant (VI) is blended with polypropylene 1:4, its limited oxygen index (LOI) after measured Being 41.82%, UL-94 vertical combustion test flame retardant rating reaches V-0 level.

Claims (9)

1. one kind containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, it is characterised in that described fire retardant be Cyanuric Chloride respectively with 1-epoxide phospha-4-methylol-2, the replacement of 6,7-trioxa-l-phosphabicyclos [2.2.2] octane one, phenyl class diamidogen one replacement, and make triazine ring The polymeric reaction product being connected.
The most according to claim 1 containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, it is characterised in that described phenyl ring class Diamidogen is p-phenylenediamine, p dimethylamine, 2,4 di amino toluene, 2,6-diaminotoluene, 4,4'-benzidine or 4,4'-bis- Diaminodiphenylmethane.
The most according to claim 2 containing polymerization macro molecular triazine ring halogen-free expansion fire retardant, it is characterised in that described phenyl ring class When diamidogen is p-phenylenediamine, fire retardant concrete structure formula is:
When described phenyl ring class diamidogen is p dimethylamine, fire retardant concrete structure formula is:
When described phenyl ring class diamidogen is 2,4 di amino toluene, fire retardant concrete structure formula is:
Described phenyl ring class diamidogen is 2, and during 6-diaminotoluene, fire retardant concrete structure formula is:
Described phenyl ring class diamidogen is 4, and during 4'-benzidine, fire retardant concrete structure formula is:
Described phenyl ring class diamidogen is 4, and during 4'-MDA, fire retardant concrete structure formula is:
4. the preparation method containing polymerization macro molecular triazine ring halogen-free expansion fire retardant as claimed in claim 1, it is characterised in that Comprise the following steps:
1) add Cyanuric Chloride and solvent, stirring in a kettle., make Cyanuric Chloride dispersed, control to drip at-5 DEG C~5 DEG C Add and drip 1-epoxide phospha-4-methylol-2,6,7-trioxa-l-phosphabicyclos [2.2.2] octane and acid binding agent so that solution ph is 5~8, Reacting 3~4 hours after being added dropwise to complete, pH stable is 7~8, and reaction separates after terminating, and obtains intermediate product one;
2) temperature is increased to 40 DEG C~55 DEG C, stirring so that intermediate product one uniform distribution in a solvent, continues to control dropping benzene Ring class diamidogen and acid binding agent so that pH value is 5~8, react 6~8 hours after being added dropwise to complete, pH stable is 7~8, instead Should separate after terminating, obtain intermediate product two;
3) temperature is increased to 95 DEG C~105 DEG C, stirring so that intermediate product two uniform distribution in a solvent, continues to control dropping Phenyl ring class diamidogen and acid binding agent so that pH value is 5~8, react 10~12 hours after being added dropwise to complete, pH stable 7~8, Reaction separates after terminating, and obtains containing polymerization macro molecular triazine ring halogen-free expansion fire retardant.
Preparation method the most according to claim 4, it is characterised in that described acid binding agent is sodium bicarbonate, sodium carbonate, hydroxide Sodium, potassium hydroxide, triethylamine, pyridine, triethylene diamine, N-methylmorpholine, tetramethylethylenediamine, 1,8-diazabicylo ten One carbon-7-alkene or DMAP.
Preparation method the most according to claim 5, it is characterised in that described acid binding agent is sodium bicarbonate or triethylamine.
Preparation method the most according to claim 4, it is characterised in that described phenyl ring class diamidogen be p-phenylenediamine, p dimethylamine, 2,4 di amino toluene, 2,6-diaminotoluene, 4,4'-benzidine or 4,4'-MDA.
Preparation method the most according to claim 4, it is characterised in that step 1) and step 2) described in solvent be acetone and The volume ratio of the mixture of water, acetone and water is 1:1~1.5.
Preparation method the most according to claim 4, it is characterised in that step 3) described in solvent be toluene.
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CN109111571A (en) * 2018-07-19 2019-01-01 顺德职业技术学院 Containing triazine-phosphorus schiff bases fire retardant and its synthetic method
CN109705607A (en) * 2019-01-04 2019-05-03 昆山阿基里斯人造皮有限公司 Flexible PVC fire retardant and preparation method thereof
CN112608485A (en) * 2020-11-25 2021-04-06 华东理工大学 Organic-inorganic hybrid efficient synergistic flame-retardant char-forming agent and preparation method thereof

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