CN106045928A - Method for preparing triazine ring carbon-forming agent containing polyhydroxyl - Google Patents
Method for preparing triazine ring carbon-forming agent containing polyhydroxyl Download PDFInfo
- Publication number
- CN106045928A CN106045928A CN201610368748.6A CN201610368748A CN106045928A CN 106045928 A CN106045928 A CN 106045928A CN 201610368748 A CN201610368748 A CN 201610368748A CN 106045928 A CN106045928 A CN 106045928A
- Authority
- CN
- China
- Prior art keywords
- forming agent
- added dropwise
- triazine ring
- acid binding
- binding agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JWGFFLADUZNCGE-UHFFFAOYSA-N [O-][N+](CCN(CCO)c1nc(N(CCO)CCO)nc(NCCO)n1)=O Chemical compound [O-][N+](CCN(CCO)c1nc(N(CCO)CCO)nc(NCCO)n1)=O JWGFFLADUZNCGE-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for preparing a triazine ring carbon-forming agent containing polyhydroxyl. A synthesized polyol triazine ring is a haplotype expansive type flame-retardant carbon-forming agent integrating air sources and carbon sources onto single molecules. The preparation method comprises the following steps: a step 1) of adding cyanuric chloride and a solvent into a reaction kettle, performing stirring and dispersion, controlling diethanolamine and an acid binding agent which are added dropwise to make the pH value of the solution be 5-8, and reacting for 3-4 h after the dropwise adding to obtaining a first intermediate product; a step 2) of warming to 40-55 DEG C, performing stirring, continuing to control diethanolamine and the acid binding agent which are added dropwise to make the pH be 5-8, reacting for 6-8 h after the dropwise adding to stabilize the pH to be 7-8, and obtaining a second intermediate product; a step 3) of warming to 85-105 DEG C, performing stirring, continuing to control diethanolamine and the acid binding agent which are added dropwise to make the pH be 5-8, reacting for 10-12 h after the dropwise adding to stabilize the pH to be 7-8, and obtaining the triazine ring carbon-forming agent containing polyhydroxyl.
Description
Technical field
The present invention relates to the preparation method of a kind of carbon forming agent, become carbon more specifically to one containing polyhydric triazine ring
The preparation method of agent.
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 suitable
The advantages such as Ying Xingguang, have captured most of polymer flame retardant market.But generate when the shortcoming of halogen flame is burning
Substantial amounts of cigarette and poisonous and there is corrosive gas, big to environment and harm, therefore the most a lot of fields limit right
The application of halogen flame.
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) to expansion flame-retardant polypropylene
The research of alkene, opens up a new way for the development of flame retardance of polymer technology.Expansion type flame-retardant polymer have high flame retardant,
Behavior without molten drop, has fabulous repellence to long-time or repeated exposure in flame；Halogen, non-oxidation antimony；Low cigarette, low toxicity,
The advantages such as non-corrosiveness gas.Therefore the revolution of flame-retarded technology it is described as.Expansion type flame retardant (Intumescent
Flame Retardant, IFR) it is a kind of novel halogen-free flame retardants, because of its gas harmless of release, neat coal amout when burning
Layer of charcoal that is big and that generate can be effectively prevented the advantages such as polymer molten drop, is particularly well-suited to the fire-retardant of polymer.So, expand
Type fire retardant flame retardant area at home and abroad increasingly comes into one's own.It is gentle that expansion type flame retardant system mainly contains acid source, carbon source
Source three class component.In traditional expansion type flame retardant system, general many with APP (APP), polyhydric alcohol and Cyanuric Chloride
Compounding ingredients forms, and therefore, generally believes that the fire retardant mechanism of intumescent system is: APP decomposes, generates and has strong taking off
The phosphoric acid of water effect and pyrophosphoric acid, make tetramethylolmethane (PER) be esterified, and then dehydration carbonization.The steam of reaction formation and triazine
The ammonia that ring decomposes makes layer of charcoal expand, and ultimately forms one layer of microporous carbon-coating, thus completely cuts off air and heat transfer, protection polymerization
Owner's body, reaches fire-retardant purpose.Theoretically, following step is mainly experienced in the formation of foamed char: (l) lower temperature
Under (about 150 DEG C), acid source releasing can esterification polyol and can be as the mineral acid of dehydrant；(2) at slightly higher temperature, inorganic
Acid and polyhydric alcohol (carbon source) carry out esterification, and the amine in system, then as the catalyst of esterification, makes esterification add
Speed is carried out；(3) system melts before esterification or in esterification；(4) in course of reaction produce water vapour and by source of the gas
Producing non-flammable gases makes the system being in molten condition expanded foamed.Meanwhile, polyhydric alcohol and ester dehydration carbonization, formed
Inorganic matter and charcoal residue, and system is the most expanded foamed；(5) when reaction is nearly completed, system gel and solidification, last shape
Become 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 burning
During, become charcoal that the anti-flammability of polymer is had the biggest impact.Therefore, develop efficient carbon forming agent, particularly can
Promote that polymer self more participates in into the expansion type flame retardant of charcoal, be significant.Triazine system derivant is one big
Class, rich in the compound of tertiary carbon structure, has excellent charred effect.Three chlorine atoms in Cyanuric Chloride at different temperatures,
Reactivity is different.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 based on pyrrolotriazine derivatives
Compound is as the novel carbon forming agent in IFR system, it has proved that the fire retardation improving IFR is had significant cooperative effect.
Triazine system derivant its be mainly characterized by from its starting material Cyanuric Chloride, and containing the most isoplastic compound react, can
To synthesize multiple compounds, it mainly has the advantage that (1) Halogen, low toxicity；(2) decomposition temperature is high；(3) physics to material
Mechanical impact is little；(4) exudation；(5) flame retarding efficiency is high.
The acid reaction that polyhydric alcohol in expansion type flame retardant discharges when being heated and in fire retardant generates ester, generation
The further thermal dehydration of ester forms carbon-coating.Alcohol in fire retardant is the most, and the carbon-coating that decomposes is formed is the finest and close, thus fire-retardant
Effect is the best.The Chinese patent of patent No. CN201210226879.2 discloses a kind of 2,4,6-tri-(N, N-dihydroxy ethyl) amine
The preparation method of base-1,3,5-triazines, the method utilizes the carbon forming agent 2,4 that Cyanuric Chloride is synthesized respectively with diethanolamine,
6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazines hydroxyl value is big, and nitrogen content is high, has the multi-hydroxy ethyl knot of easily cyclisation simultaneously
Structure, but the diethanolamine accessed is secondary amine, and nucleophilic displacement of fluorine ability is slightly lower, and the productivity of crucial preparation method is relatively low.Structural formula is such as:
It is thus desirable to develop a kind of new preparation method to solve problems of the prior art with not enough.
Summary of the invention
It is an object of the invention to provide a kind of preparation method containing polyhydric triazine ring carbon forming agent, the preparation of the present invention
Method make use of the feature that primary amine reaction activity is high, introduces primary amine alcohol and reacts with Cyanuric Chloride, and each triazine monocycle contains at least 4
Individual hydroxyl, hydroxyl value is big, can do response type expansion type flame-retarding carbon forming agent, and its synthesized polyhydric alcohol triazine ring is collection source of the gas, carbon source
Haplotype expansion type flame-retarding carbon forming agent on single molecule.
The present invention's is the product of Cyanuric Chloride and hydramine containing polyhydric triazine ring carbon forming agent.Can be three polychlorostyrene
Cyanogen respectively with two replacements, a substitution reaction product of ethanolamine of diethanolamine, concrete product structural formula is:
Can also be Cyanuric Chloride respectively with two replacements, a substitution reaction product of para-aminophenol of diethanolamine, tool
Precursor reactant product structure formula is:
Can also is that Cyanuric Chloride respectively with two replacements, a substitution reaction product of Ortho-Aminophenol of diethanolamine, tool
Precursor reactant product structure formula is:
Can also is that Cyanuric Chloride produces with two replacements of diethanolamine, a substitution reaction of 2-phenyldiethanol-amine respectively
Thing, concrete product structural formula is:
Can also is that Cyanuric Chloride respectively with two replacements, a substitution reaction product of diglycolamine of diethanolamine, specifically
Product structural formula is:
Can also is that Cyanuric Chloride respectively with two replacements, a substitution reaction product of monoisopropanolamine of diethanolamine, tool
Precursor reactant product structure formula is:
The present invention is achieved by the following technical solutions:
The preparation method containing polyhydric triazine ring carbon forming agent of the present invention, it comprises the following steps:
1) add Cyanuric Chloride and solvent, stirring in a kettle., make Cyanuric Chloride dispersed, at-5 DEG C～5 DEG C
Controlling dropping diethanolamine and acid binding agent so that solution ph is 5～8, react 3～4 hours after being added dropwise to complete, pH stable exists
7～8, 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 to drip
Adding diethanolamine 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 85 DEG C～105 DEG C, stirring so that intermediate product two uniform distribution in a solvent, continues to control
Dropping hydramine and acid binding agent so that pH value is 5～8, reacts 10～12 hours after being added dropwise to complete, pH stable is 7～8, instead
Should separate after terminating, obtain containing polyhydric triazine ring carbon forming agent.
The preparation method that the present invention is above-mentioned, its further technical scheme be described acid binding agent be sodium bicarbonate, carbonic acid
Sodium, sodium hydroxide, potassium hydroxide, triethylamine, pyridine, triethylene diamine, N-methylmorpholine, tetramethylethylenediamine, 1,8-phenodiazine
Miscellaneous bicyclo-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 step 3) described in hydramine be second
Hydramine, diethanolamine, para-aminophenol, Ortho-Aminophenol, diglycolamine, normal propyl alcohol amine or isopropanolamine.
The preparation method that the present invention is above-mentioned, its further technical scheme can also is that described solvent is acetone and water
The volume ratio of mixture, acetone and water is 1:1～1.5.
The carbon forming agent present invention obtained compounds with phosphorus series compound, can obtain different types of expansion type flame retardant.This
The bright flame-retardant polymer to using the inventive method to prepare is not particularly limited.Can formula, physical mixed routinely.Hereby
It is applicable to various thermoplastic polymer such as polypropylene, polyethylene, polrvinyl chloride, polystyrene, polymethyl methacrylate, polyamides
Amine, Merlon, poly-terephthalate analog thermoplastic polyester etc.；Can also be used for various thermosetting resin, such as epoxy resin, poly-ammonia
Ester etc. do firming agent or auxiliary agent uses.
Compared with prior art beneficial effects of the present invention is as follows:
The present invention utilizes the 3rd chlorine atom of Cyanuric Chloride to need the condition of pyroreaction, introduces the primary amine that activity is bigger, phase
Than the 3rd the chlorine atom utilizing secondary amine diethanolamine to react Cyanuric Chloride in patent CN201210226879.2, obtain product
2,4,6-tri-(N, N-dihydroxy ethyl) amido-1,3,5-triazine productivity is greatly improved.
In the present invention, the macro molecular triazine class carbon forming agent of preparation is white solid, uses synthetic method to prepare, this conjunction
Becoming course of reaction continuous, synthesis technique is simple, and generated time is it is generally required to 15 to 25 hours.It addition, prepared by the present invention big point
Sub-triazines carbon forming agent Heat stability is good, residual chlorine content is below 2.5%.With above-mentioned unimolecule triazines carbon forming agent for becoming charcoal
Agent component, to some compound modified prepared expansion type flame retardants, the feature of environmental protection and anti-flammability are relatively good, and neat coal amout is big, covering
Rate is high.
Detailed description of the invention
Embodiment 1
18.45g is added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer
Cyanuric Chloride and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed,
Then, under conditions of 0 DEG C, 10.5g diethanolamine and NaHCO the most uniformly it are slowly added dropwise3Solution (8.4g NaHCO3Molten
Solution is in 100ml distilled water), after dropping, react 3 hours under conditions of 0 DEG C.Then liter high-temperature is to 40 DEG C, adds
100ml acetone soln, then in reaction bulb, uniformly it is slowly added dropwise 10.5g diethanolamine and NaHCO3Solution (8.4g NaHCO3Molten
Solution is in 100ml distilled water), keep temperature 40 DEG C, after dropping, then react 8 hours under the conditions of this.Then 60 it are warming up to
DEG C, steam acetone, then proceed to be warming up to 85 DEG C, in reaction bulb, be uniformly slowly added dropwise 8g ethanolamine and NaHCO3Solution
(8.4gNaHCO3It is dissolved in 100ml distilled water), it is stirred at reflux reaction 12 hours, product is steamed drying after terminating by reaction,
Again with ethanol solution washing, sucking filtration, then filtrate being steamed drying, obtain containing polyhydric triazine ring carbon forming agent (I), its productivity is
92.43%.Its structural formula is:
When triazine ring carbon forming agent (I) and APP (APP), polypropylene 0.75:0.25:4 are blended, its limit after measured
Oxygen index (OI) (LOI) is 36.59%, and UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 2
18.45g is added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer
Cyanuric Chloride and 100ml acetone soln (volume ratio of acetone and water is 1:1.5), be sufficiently stirred for, make Cyanuric Chloride dispersion all
Even, then under conditions of-5 DEG C, the most uniformly it is slowly added dropwise 10.5g diethanolamine and triethylamine solution (10.1g tri-second
Amine solvent is in 100ml distilled water), after dropping, react 4 hours under conditions of-5 DEG C.Then liter high-temperature is to 50 DEG C,
Add 100ml acetone soln, then in reaction bulb, be uniformly slowly added dropwise 10.5g diethanolamine and triethylamine solution (10.1g tri-second
Amine solvent is in 100ml distilled water), keep temperature 50 C, after dropping, then react 6 hours under the conditions of this.Then it is warming up to
60 DEG C, steam acetone, then proceed to be warming up to 99 DEG C, in reaction bulb, be uniformly slowly added dropwise 13g para-aminophenol and triethylamine
Solution (10.1g triethylamine is dissolved in 100ml distilled water), is stirred at reflux reaction 11 hours, and product is steamed after terminating by reaction
Dry, then with ethanol solution washing, sucking filtration, then filtrate is steamed drying, obtain, containing polyhydric triazine ring carbon forming agent (II), producing
Rate 80.11%.Its structural formula is:
When triazine ring carbon forming agent (II) and APP (APP), polypropylene 0.75:0.25:4 are blended, its pole after measured
Limited oxygen index (LOI) is 31.12%, and UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 3
18.45g is added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer
Cyanuric Chloride and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed,
Then, under conditions of 5 DEG C, 10.5g diethanolamine and NaHCO the most uniformly it are slowly added dropwise3Solution (8.4g NaHCO3Molten
Solution is in 100ml distilled water), after dropping, react 3 hours under conditions of 5 DEG C.Then liter high-temperature is to 45 DEG C, adds
100ml acetone soln, then in reaction bulb, uniformly it is slowly added dropwise 10.5g diethanolamine and NaHCO3Solution (8.4g NaHCO3Molten
Solution is in 100ml distilled water), keep temperature 45 C, after dropping, then react 7 hours under the conditions of this.Then 60 it are warming up to
DEG C, steam acetone, then proceed to be warming up to 105 DEG C, in reaction bulb, be uniformly slowly added dropwise 13g Ortho-Aminophenol and NaHCO3
Solution (8.4gNaHCO3It is dissolved in 100ml distilled water), it is stirred at reflux reaction 10 hours, product is steamed baking after terminating by reaction
Dry, then with ethanol solution washing, sucking filtration, then filtrate is steamed drying, obtain containing polyhydric triazine ring carbon forming agent (III), productivity
It is 92.16%.Its structural formula is:
When triazine ring carbon forming agent (III) and APP (APP), polypropylene 0.75:0.25:4 are blended, its pole after measured
Limited oxygen index (LOI) is 34.07%, and UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 4
18.45g is added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer
Cyanuric Chloride and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed,
Then, under conditions of 0 DEG C, (10.1g triethylamine is molten to be the most uniformly slowly added dropwise 10.5g diethanolamine and triethylamine solution
Solution is in 100ml distilled water), after dropping, react 3 hours under conditions of 0 DEG C.Then liter high-temperature is to 40 DEG C, adds
100ml acetone soln, then (10.1g triethylamine is molten to be uniformly slowly added dropwise 10.5g diethanolamine and triethylamine solution in reaction bulb
Solution is in 100ml distilled water), keep temperature 40 DEG C, after dropping, then react 8 hours under the conditions of this.Then 60 it are warming up to
DEG C, steam acetone, then proceed to be warming up to 85 DEG C, in reaction bulb, be uniformly slowly added dropwise 13.7g 2-phenyldiethanol-amine and three
Ethylamine solution (10.1g triethylamine is dissolved in 100ml distilled water), is stirred at reflux reaction 12 hours, reacts product after terminating
Steam drying, then with ethanol solution washing, sucking filtration, then filtrate is steamed drying, obtain containing polyhydric triazine ring carbon forming agent
(IV), its productivity is 84.25%.Its structural formula is:
When triazine ring carbon forming agent (IV) and APP (APP), polypropylene 0.75:0.25:4 are blended, its pole after measured
Limited oxygen index (LOI) is 37.61%, and UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 5
18.45g is added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer
Cyanuric Chloride and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed,
Then, under conditions of 5 DEG C, 10.5g diethanolamine and NaHCO the most uniformly it are slowly added dropwise3Solution (8.4g NaHCO3Molten
Solution is in 100ml distilled water), after dropping, react 3 hours under conditions of 5 DEG C.Then liter high-temperature is to 45 DEG C, adds
100ml acetone soln, then in reaction bulb, uniformly it is slowly added dropwise 10.5g diethanolamine and NaHCO3Solution (8.4g NaHCO3Molten
Solution is in 100ml distilled water), keep temperature 45 C, after dropping, then react 7 hours under the conditions of this.Then 60 it are warming up to
DEG C, steam acetone, then proceed to be warming up to 105 DEG C, in reaction bulb, be uniformly slowly added dropwise 10.5g diglycolamine and NaHCO3Molten
Liquid (8.4g NaHCO3It is dissolved in 100ml distilled water), it is stirred at reflux reaction 10 hours, product is steamed baking after terminating by reaction
Dry, then with ethanol solution washing, sucking filtration, then filtrate is steamed drying, obtain containing polyhydric triazine ring carbon forming agent (V), productivity
It is 87.27%.Its structural formula is:
When triazine ring carbon forming agent (V) and APP (APP), polypropylene 0.75:0.25:4 are blended, its pole after measured
Limited oxygen index (LOI) is 33.59%, and UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Embodiment 6
18.45g is added in equipped with the 1L reaction flask of reflux condensing tube, constant pressure funnel, agitator and thermometer
Cyanuric Chloride and 100ml acetone soln (volume ratio of acetone and water is 1:1), be sufficiently stirred for, make Cyanuric Chloride be uniformly dispersed,
Then, under conditions of 0 DEG C, (10.1g triethylamine is molten to be the most uniformly slowly added dropwise 10.5g diethanolamine and triethylamine solution
Solution is in 100ml distilled water), after dropping, react 3 hours under conditions of 0 DEG C.Then liter high-temperature is to 40 DEG C, adds
100ml acetone soln, then (10.1g triethylamine is molten to be uniformly slowly added dropwise 10.5g diethanolamine and triethylamine solution in reaction bulb
Solution is in 100ml distilled water), keep temperature 40 DEG C, after dropping, then react 8 hours under the conditions of this.Then 60 it are warming up to
DEG C, steam acetone, then proceed to be warming up to 85 DEG C, in reaction bulb, be uniformly slowly added dropwise 7.5g monoisopropanolamine and triethylamine is molten
Liquid (10.1g triethylamine is dissolved in 100ml distilled water), is stirred at reflux reaction 12 hours, and product is steamed baking after terminating by reaction
Dry, then with ethanol solution washing, sucking filtration, then filtrate is steamed drying, and obtain containing polyhydric triazine ring carbon forming agent (VI), it produces
Rate is 88.42%.Its structural formula is:
When triazine ring carbon forming agent (VI) and APP (APP), polypropylene 0.75:0.25:4 are blended, its pole after measured
Limited oxygen index (LOI) is 35.16%, and UL-94 vertical combustion test flame retardant rating reaches V-0 level.
Claims (5)
1. the preparation method containing polyhydric triazine ring carbon forming agent, it is characterised in that comprise the following steps:
1) add Cyanuric Chloride and solvent, stirring in a kettle., make Cyanuric Chloride dispersed, control at-5 DEG C～5 DEG C
Dropping diethanolamine and acid binding agent so that solution ph is 5～8, reacts 3～4 hours after being added dropwise to complete, pH stable 7～
8, 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 two
Ethanolamine and acid binding agent so that pH value is 5～8, react 6～8 hours after being added dropwise to complete, pH stable 7～8, reaction knot
Separate after bundle, obtain intermediate product two；
3) temperature is increased to 85 DEG C～105 DEG C, stirring so that intermediate product two uniform distribution in a solvent, continues to control dropping
Hydramine 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 knot
Separate after bundle, obtain containing polyhydric triazine ring carbon forming agent.
Preparation method the most according to claim 1, it is characterised in that described acid binding agent is sodium bicarbonate, sodium carbonate, hydrogen
Sodium oxide, potassium hydroxide, triethylamine, pyridine, triethylene diamine, N-methylmorpholine, tetramethylethylenediamine, 1,8-diazabicylo
11 carbon-7-alkene or DMAPs.
Preparation method the most according to claim 2, it is characterised in that described acid binding agent is sodium bicarbonate or triethylamine.
Preparation method the most according to claim 1, it is characterised in that step 3) described in hydramine be ethanolamine, diethanol
Amine, para-aminophenol, Ortho-Aminophenol, diglycolamine, normal propyl alcohol amine or isopropanolamine.
Preparation method the most according to claim 1, it is characterised in that described solvent is the mixture of acetone and water, acetone
It is 1:1～1.5 with the volume ratio of water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610368748.6A CN106045928A (en) | 2016-05-30 | 2016-05-30 | Method for preparing triazine ring carbon-forming agent containing polyhydroxyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610368748.6A CN106045928A (en) | 2016-05-30 | 2016-05-30 | Method for preparing triazine ring carbon-forming agent containing polyhydroxyl |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106045928A true CN106045928A (en) | 2016-10-26 |
Family
ID=57176037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610368748.6A Pending CN106045928A (en) | 2016-05-30 | 2016-05-30 | Method for preparing triazine ring carbon-forming agent containing polyhydroxyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106045928A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603068A (en) * | 2017-10-12 | 2018-01-19 | 钱艺博 | A kind of polyvinyl chloride carbonized agent and preparation method thereof |
| CN108384001A (en) * | 2018-03-17 | 2018-08-10 | 山东兄弟科技股份有限公司 | Primary amine blocking modification macro molecular triazine carbon forming agent and preparation method thereof |
| CN109705942A (en) * | 2019-02-28 | 2019-05-03 | 盘锦辽河油田大力集团有限公司 | A kind of preparation method of steric hindrance amine type desulfurization and decarburization agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110178212A1 (en) * | 2008-03-31 | 2011-07-21 | Borealis Agrolinz Melamine Gmbh | Method for Producing a Compound with at Least One at Least Monosubstituted Amino Group |
| CN102181073A (en) * | 2011-02-14 | 2011-09-14 | 福建师范大学 | Triazine compound coordination crosslinking synergistic agent for elastomer and preparation method thereof |
| CN102731422A (en) * | 2012-06-29 | 2012-10-17 | 福建工程学院 | Preparation method of 6-(N,N-dihydroxyethyl)amino-2,4-dichloro-1,3,5-triazine |
| CN102757394A (en) * | 2012-06-29 | 2012-10-31 | 福建师范大学 | Preparation method of 2,4,6-tri(N,N-diethoxyl)amino-1,3,5-triazine |
-
2016
- 2016-05-30 CN CN201610368748.6A patent/CN106045928A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110178212A1 (en) * | 2008-03-31 | 2011-07-21 | Borealis Agrolinz Melamine Gmbh | Method for Producing a Compound with at Least One at Least Monosubstituted Amino Group |
| CN102181073A (en) * | 2011-02-14 | 2011-09-14 | 福建师范大学 | Triazine compound coordination crosslinking synergistic agent for elastomer and preparation method thereof |
| CN102731422A (en) * | 2012-06-29 | 2012-10-17 | 福建工程学院 | Preparation method of 6-(N,N-dihydroxyethyl)amino-2,4-dichloro-1,3,5-triazine |
| CN102757394A (en) * | 2012-06-29 | 2012-10-31 | 福建师范大学 | Preparation method of 2,4,6-tri(N,N-diethoxyl)amino-1,3,5-triazine |
Non-Patent Citations (1)
| Title |
|---|
| 陈荣国等，: "双亲羟烷胺基-1,3,5-三嗪的合成与表征", 《福建师范大学学报(自然科学版)》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603068A (en) * | 2017-10-12 | 2018-01-19 | 钱艺博 | A kind of polyvinyl chloride carbonized agent and preparation method thereof |
| CN108384001A (en) * | 2018-03-17 | 2018-08-10 | 山东兄弟科技股份有限公司 | Primary amine blocking modification macro molecular triazine carbon forming agent and preparation method thereof |
| CN108384001B (en) * | 2018-03-17 | 2020-05-22 | 山东兄弟科技股份有限公司 | Primary amine end-capped modified macromolecule triazine charring agent and preparation method thereof |
| CN109705942A (en) * | 2019-02-28 | 2019-05-03 | 盘锦辽河油田大力集团有限公司 | A kind of preparation method of steric hindrance amine type desulfurization and decarburization agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107118347B (en) | " Trinity " expansion type flame retardant and its synthetic method | |
| CN105924645A (en) | Halogen-free expanding flame retardant containing polymeric macromolecule triazine rings and preparation method of halogen-free expanding flame retardant | |
| CN100463952C (en) | Triazine ring combustion inhibitor containing phosphorus and its preparing process | |
| CN105348326B (en) | A kind of N P fire proofings and preparation method thereof and the application in textile | |
| CN103113619B (en) | Triazine ring containing caged organic phosphate flame retardant and preparation method thereof | |
| CN105440308A (en) | High phosphorus-nitrogen content flame retardant and preparation method thereof | |
| CN108864193B (en) | Phosphaphenanthrene compound, and preparation method and application thereof | |
| CN104558684A (en) | DOPO-containing dioxacaprophosphate flame retardant as well as preparation method and application thereof | |
| CN105968410B (en) | One kind containing polyhydroxy, phosphorus system triazine ring expansion type flame retardant and preparation method | |
| CN103113409A (en) | Triazine ring structure containing caged organic phosphate and preparation method thereof | |
| CN106045928A (en) | Method for preparing triazine ring carbon-forming agent containing polyhydroxyl | |
| CN105295093A (en) | Ring phosphonitrile type additive flame retardant and preparation method thereof | |
| CN104693770A (en) | Halogen-free expansion type flame-retardant polycarbonate composite material and preparation method thereof | |
| CN110643066A (en) | Novel phosphorus-nitrogen flame retardant and preparation method thereof | |
| CN102225998A (en) | Preparation method for pentaerythritol phosphoryl triethanolamide | |
| CN106916188A (en) | 2,4,6 3 (the dimethyl phosphate base amido) melamine salts of 1,3,5 triazine three and preparation and application | |
| CN107056839A (en) | A kind of synthetic method of novel reaction type bicyclic phosphate fire retardant | |
| CN104403106A (en) | Polymeric phosphorus nitrogen expansion type flame retardant agent and preparation method thereof | |
| CN108951164A (en) | A kind of pure cotton fabric antiflaming finishing agent and preparation method thereof | |
| CN109796496B (en) | Three phosphazene derivative of ring containing alkoxy and its preparation method and application | |
| CN106009039A (en) | Flame-retardant agent containing spirane structure and having antioxidant function and preparation method | |
| CN104031090B (en) | A kind of preparation method of ring-type phosphorus nitrogen synergistic halogen-free flame retardants | |
| CN105968408A (en) | Intumescent flame retardant containing polyhydroxy groups and two triazine rings and preparation method | |
| CN102604157B (en) | Flame retardant and preparation method thereof | |
| CN106892943B (en) | A kind of compound in triazine class, preparation method and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161026 |