CN106046049B - Benzylamine-N, N- dimethylene phosphonic acids melamine salt and preparation method and application - Google Patents
Benzylamine-N, N- dimethylene phosphonic acids melamine salt and preparation method and application Download PDFInfo
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- CN106046049B CN106046049B CN201610514639.0A CN201610514639A CN106046049B CN 106046049 B CN106046049 B CN 106046049B CN 201610514639 A CN201610514639 A CN 201610514639A CN 106046049 B CN106046049 B CN 106046049B
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- Prior art keywords
- benzylamine
- phosphonic acids
- dimethylene phosphonic
- dimethylene
- melamine
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 36
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 15
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 24
- -1 dimethylene phosphonic acids melamine salts Chemical class 0.000 abstract description 17
- 238000010992 reflux Methods 0.000 abstract description 17
- 239000007787 solid Substances 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000008367 deionised water Substances 0.000 abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 6
- 235000019504 cigarettes Nutrition 0.000 abstract description 5
- 239000005457 ice water Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 238000012827 research and development Methods 0.000 abstract description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3817—Acids containing the structure (RX)2P(=X)-alk-N...P (X = O, S, Se)
-
- 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
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a kind of benzylamine N, N dimethylene phosphonic acids melamine salts and preparation method and application, the reaction ratio of benzylamine N, N dimethylene phosphonic acids and melamine is 1.0 in molar ratio:1.0~5.0, benzylamine N, N the dimethylene phosphonic acids is by benzylamine, formaldehyde and phosphorous acid according to molar ratio 0.5~1.5:1.0~5.0:1.0~5.0 reactions are made, and preparation method is：Benzylamine, formaldehyde and phosphorous acid are separately added into, reaction is heated to reflux, and question response terminates, and respectively with diluted acid and washing, obtains benzylamine N, N dimethylene phosphonic acids；Benzylamine N, N dimethylene phosphonic acids and melamine are added, adds deionized water and n,N dimethylformamide, it is stirred at reflux, question response terminates, and products therefrom is cooled down with ice-water bath, filters, washing, dry white solid, is benzylamine N, N dimethylene phosphonic acids melamine salt.Benzylamine N, N dimethylene phosphonic acids melamine salt has the advantages that low cigarette, low toxicity, non-corrosiveness gas produce, is environmentally friendly, efficient, meets the research and development direction of following fire retardant.
Description
Technical field
The present invention relates to a kind of phosphorus-nitrogen expansion type fire retardant, and in particular to a kind of benzylamine-N, N- dimethylenes phosphonic acids three
Paracyanogen amine salt and preparation method and application.
Background technology
Traditional fire retardant since there are halogen atom, additive amount is big, smoke amount is big, easily produce it is poisonous, be corrosive
The wretched insufficiencies such as gas are just substituted by new generation of environment protection fire retardant, the surface meeting in burning of the matrix containing expansion type flame retardant
Carbonaceous froth bed is generated, plays heat-insulated, oxygen barrier, suppression cigarette, antidrip and other effects, there is excellent fire resistance, and it is low cigarette, low
Poison, non-corrosiveness gas produce, and phosphorus-nitrogen expansion type fire retardant is then the important research direction of environment friendly flame retardant, it is also
Realize one of non-halogen effective way of fire retardant.
Phosphorus-nitrogen expansion type fire retardant has the advantages that low toxicity, low-smoke and without molten drop, has been widely used in polymerizeing
Thing it is fire-retardant, and show good flame retardant effect.Meanwhile phosphorus-nitrogen expansion type fire retardant is usually by acid source, charcoal source and source of the gas
Three parts form, and when heated, fine and close porous foam layer of charcoal can be formed in polymer surfaces, which can both prevent internal layer base
The further degraded of body material, and the transmission of heat and oxygen to basis material can be prevented, so as to play fire retardation.Phosphorus-nitrogen
Expansion type fire retardant meets the research and development direction of following fire retardant, is a kind of environmentally friendly Green Flammability agent, has become state
One of inside and outside fire retardant research field the most active.
The content of the invention
Problem to be solved by this invention is to propose a kind of benzylamine-N for the above-mentioned prior art, N- dimethylene phosphonic acids
Melamine salt and preparation method and application, it is phosphorus-nitrogen expansion type fire retardant, has excellent heat endurance, very high
The features such as acid source of content, higher charring rate, good flame-retardant smoke inhibition effect and low toxicity, non-corrosiveness gas produce, symbol
The requirement of environmental protection is closed, is the important development direction of expansion type flame retardant.
Technical solution provided by the invention is：
A kind of benzylamine-N, N- dimethylene phosphonic acids melamine salt, it is by benzylamine-N, N- dimethylenes phosphonic acids and melamine
Amine reaction is made, and the reaction ratio of benzylamine-N, N- dimethylene phosphonic acids and melamine is 1.0 in molar ratio:1.0~5.0, institute
Benzylamine-N, N- the dimethylene phosphonic acids stated is by benzylamine, formaldehyde and phosphorous acid according to molar ratio 0.5~1.5:1.0~5.0:1.0~
5.0 reactions are made.
Benzylamine-N, N- the dimethylene phosphonic acids is calculated as benzylamine, formaldehyde and phosphorous acid=0.5 by mol ratio:1.0:
1.0 reactions are made.
The preparation method of benzylamine-N, N- the dimethylene phosphonic acids melamine salt, includes following steps：
(1) it is prepared by benzylamine-N, N- dimethylene phosphonic acids
By 1.0~5.0 ︰ 1.0~5.0 of molar ratio=0.5~1.5 ︰ of Bian An ︰ Jia Quan ︰ phosphorous acid, prepare benzylamine, formaldehyde
It is spare with phosphorous acid；In the three-necked bottle equipped with reflux, agitating device and constant pressure funnel, benzylamine, Asia are separately added into
Phosphoric acid and formaldehyde, react and are persistently stirred at reflux 20~24h, after question response, are cooled to room temperature, separate out a large amount of solids, respectively
Washed with dilute hydrochloric acid and deionized water, it is dry, white solid is obtained, is benzylamine-N, N- dimethylene phosphonic acids；
(2) preparation of benzylamine-N, N- dimethylene phosphonic acids melamine salt
By benzylamine-N, molar ratio=1.0 of N- dimethylene Lin Suan ﹕ melamines:1.0~5.0, preparation process (1) institute
Benzylamine-N, N- the dimethylene phosphonic acids and melamine obtained is spare；At 25~80 DEG C, equipped with agitating device and reflux
There-necked flask in, be separately added into benzylamine-N, N- dimethylene phosphonic acids and melamine, add deionized water and N, N dimethyl
Formamide, is stirred at reflux 7~10h, and after question response, products therefrom is cooled down with ice-water bath, filters, washing, dry to perseverance
Weight, obtains white solid, is benzylamine-N, N- dimethylene phosphonic acids melamine salt.
The structural formula of benzylamine-N of the present invention, N- dimethylene phosphonic acids melamine salt is as follows：
Its react basic principle be：
It is of the invention to be had the following advantages compared with existing fire retardant technology：Compared with the fire retardant used in general technology,
Benzylamine-N, N- dimethylene phosphonic acids melamine salt fire retardant overcomes big general fire retardant additive amount, generation smog, produces corruption
Corrosion gas, the mechanical property for the material that give off poisonous gas, influences and have the shortcomings that pollution to environment, and with less toxic, low cigarette,
The advantages that non-corrosiveness gas is released, high-efficiency environment friendly is the important development direction of following expansion type flame retardant.And in the present invention
Fire retardant has certain polymer characteristics, can be compatible well with processed matrix, and matrix physicochemical property is influenced very
It is few；Decomposable asymmetric choice net releases water when the fire retardant is heated and melamine plays back-fire relief；P-N cooperative flame retardants effect can occur when heated
Should, the carbonaceous layer of even compact can be generated in matrix surface, there is well heat-insulated, oxygen barrier, fire-retardant and suppression cigarette effect, and can have
Effect prevents melting drip phenomenon, prevents flame transmission and sprawling；The pyrolysis temperature of fire retardant and the degraded temperature by fire proofing
Degree can reach best match.
Brief description of the drawings
Fig. 1 is the infrared absorption spectroscopy of 1 gained benzylamine-N, N- dimethylene phosphonic acids melamine salt of the embodiment of the present invention
Figure.1678cm-1For the stretching vibration peak of P-OH keys, 1226cm-1For the absorption vibration peak of P=O double bonds, 1502cm-1For melamine
The stretching vibration of triazine ring, 1160cm in amine-1For the flexural vibrations of NH, 740cm-1And 714cm-1Moved for the face bending vibration of phenyl ring C-H
Peak.The presence of above-mentioned spectral peak shows to have obtained benzylamine-N, N- dimethylene phosphonic acids melamine salt.
Embodiment
Technical scheme is further described below in conjunction with specific embodiment and attached drawing：
Embodiment 1
In the three-necked bottle of the 250mL equipped with blender, reflux and agitating device, benzylamine 0.1mol and phosphorous are added
Sour 0.2mol, under agitating and heating, is added portionwise formaldehyde 0.2mol, insulated and stirred reflux 20h, is treated anti-by constant pressure funnel
After answering, it is cooled to room temperature, separates out a large amount of solids, washed respectively with dilute hydrochloric acid and deionized water, it is dry, white solid is obtained,
As benzylamine-N, N- dimethylene phosphonic acids.
By benzylamine-N obtained above, N- dimethylene phosphonic acids 0.05mol is placed in 250mL with reflux and agitating device
In three-necked bottle, 80mL deionized waters, 80mL n,N dimethylformamide (DMF) and melamine 0.05mol are added, is stirred
Flow back 7h, and after question response, products therefrom is cooled down with ice-water bath, is filtered, and washing is dry to constant weight, obtains white solid, i.e.,
For benzylamine-N, N- dimethylene phosphonic acids melamine salts.
Embodiment 2
In the three-necked bottle of the 250mL equipped with blender, reflux and agitating device, benzylamine 0.1mol and phosphorous are added
Sour 0.3mol, under agitating and heating, is added portionwise formaldehyde 0.5mol, insulated and stirred reflux 20h, is treated anti-by constant pressure funnel
After answering, it is cooled to room temperature, separates out a large amount of solids, washed respectively with dilute hydrochloric acid and deionized water, it is dry, white solid is obtained,
As benzylamine-N, N- dimethylene phosphonic acids.
By benzylamine-N obtained above, N- dimethylene phosphonic acids 0.1mol is placed in 500mL with reflux and agitating device
In three-necked bottle, 100mL deionized waters, 100mL n,N dimethylformamide (DMF) and melamine 0.2mol are added, is stirred
Reflux 7h to be mixed, after question response, products therefrom is cooled down with ice-water bath, is filtered, washing is dry to constant weight, obtains white solid,
As benzylamine-N, N- dimethylene phosphonic acids melamine salt.
Embodiment 3
In the three-necked bottle of the 250mL equipped with blender, reflux and agitating device, benzylamine 0.1mol and phosphorous are added
Sour 0.2mol, under agitating and heating, is added portionwise formaldehyde 0.4mol, insulated and stirred reflux 20h, is treated anti-by constant pressure funnel
After answering, it is cooled to room temperature, separates out a large amount of solids, washed respectively with dilute hydrochloric acid and deionized water, it is dry, white solid is obtained,
As benzylamine-N, N- dimethylene phosphonic acids.
By benzylamine-N obtained above, N- dimethylene phosphonic acids 0.1mol is placed in 500mL with reflux and agitating device
In three-necked bottle, 150mL deionized waters, 100mL n,N dimethylformamide (DMF) and melamine 0.3mol are added, is stirred
Reflux 7h to be mixed, after question response, products therefrom is cooled down with ice-water bath, is filtered, washing is dry to constant weight, obtains white solid,
As benzylamine-N, N- dimethylene phosphonic acids melamine salt.
It is main with carbon, nitrogen, phosphorus etc. in benzylamine-N, N- the dimethylene phosphonic acids melamine salt fire retardant obtained by embodiment 1
Want the percentage composition of component as follows：
| Component | C | N | P | O | H |
| Mass fraction | 34.21 | 23.27 | 14.70 | 22.79 | 5.02 |
It is main with carbon, nitrogen, phosphorus etc. in benzylamine-N, N- the dimethylene phosphonic acids melamine salt fire retardant obtained by embodiment 2
Want the percentage composition of component as follows：
| Component | C | N | P | O | H |
| Mass fraction | 32.91 | 33.26 | 11.32 | 17.54 | 4.97 |
It is main with carbon, nitrogen, phosphorus etc. in benzylamine-N, N- the dimethylene phosphonic acids melamine salt fire retardant obtained by embodiment 3
Want the percentage composition of component as follows：
| Component | C | N | P | O | H |
| Mass fraction | 32.10 | 39.51 | 9.20 | 14.25 | 4.94 |
By benzylamine-N obtained by embodiment 1, N- dimethylene phosphonic acids melamine salts fire retardant is added in polypropylene (PP)
The performance test of oxygen index (OI) and vertical combustion grade is carried out, following data are obtained through performance test：
| Additive amount/% | 5 | 10 | 15 | 20 | 25 |
| Oxygen index (OI)/% | 22.44 | 25.30 | 28.75 | 29.89 | 32.12 |
| Burn grade/V | - | V-1 | V-0 | V-0 | V-0 |
By experimental data, it can be seen that, fire retardant benzylamine-N, N- dimethylene phosphonic acids melamine salt are in oxygen index (OI) and hang down
Direct combustion is burnt has reached national standard in the important fire resistance index of grade two, obtains good flame retardant effect, Ke Yijin
One step is promoted.
This expansion type flame retardant benzylamine-N, N- dimethylene phosphonic acids melamine salt, from the structure of molecule, has abundant
Acid source, carbon source and foaming source, have excellent heat endurance, higher smoke suppressing effect, hypotoxicity into charcoal, good, symbol
Current environmental requirement is closed, is a kind of very promising expansion type flame retardant.
Claims (6)
1. benzylamine-N, N- dimethylene phosphonic acids melamine salt, it is characterised in that its by benzylamine-N, N- dimethylenes phosphonic acids with
Melamine reaction is made, and benzylamine-N, N- dimethylene phosphonic acids is 1.0 with melamine molar ratio:1.0~5.0, the benzyl
Amine-N, N- dimethylene phosphonic acids is by benzylamine, formaldehyde and phosphorous acid according to molar ratio 0.5~1.5:1.0~5.0:1.0~5.0 is anti-
It should be made.
2. benzylamine-N as claimed in claim 1, N- dimethylene phosphonic acids melamine salt, it is characterised in that the benzylamine-
N, N- dimethylene phosphonic acids are calculated as benzylamine, formaldehyde and phosphorous acid=0.5 by mol ratio:1.0:1.0 reactions are made.
3. benzylamine-N as claimed in claim 1, N- dimethylene phosphonic acids melamine salt, it is characterised in that its structural formula is such as
Under：
4. the preparation method of benzylamine-N as claimed in claim 1, N- dimethylene phosphonic acids melamine salt, includes following step
Suddenly：
(1) it is prepared by benzylamine-N, N- dimethylene phosphonic acids
By molar ratio=0.5~1.5 of Bian An ︰ Jia Quan ︰ phosphorous acid:1.0~5.0:1.0~5.0, prepare benzylamine, formaldehyde and Asia
Phosphoric acid is spare；In the three-necked bottle equipped with reflux, agitating device and constant pressure funnel, be separately added into benzylamine, formaldehyde and
Phosphorous acid, reacts and is persistently stirred at reflux 20~24h, after question response, is cooled to room temperature, separates out a large amount of solids, respectively with dilute
Hydrochloric acid and deionized water washing, it is dry, white solid is obtained, is benzylamine-N, N- dimethylene phosphonic acids；
(2) preparation of benzylamine-N, N- dimethylene phosphonic acids melamine salt
By benzylamine-N, molar ratio=1.0 of N- dimethylene Lin Suan ﹕ melamines:1.0~5.0, obtained by preparation process (1)
Benzylamine-N, N- dimethylene phosphonic acids and melamine are spare；At 25~80 DEG C, in three equipped with agitating device and reflux
In mouth bottle, benzylamine-N, N- dimethylene phosphonic acids and melamine are separately added into, adds deionized water and N, N dimethyl formyl
Amine, is stirred at reflux 7~10h, and after question response, products therefrom is cooled down with ice-water bath, filters, washing, dry to constant weight, obtains
White solid, is benzylamine-N, N- dimethylene phosphonic acids melamine salt.
5. the preparation method of benzylamine-N as claimed in claim 4, N- dimethylene phosphonic acids melamine salt, it is characterised in that
The molar ratio of the Bian An ︰ Jia Quan ︰ phosphorous acid is 0.5:1.0:1.0.
6. if claims 1 to 3 any one of them benzylamine-N, N- dimethylene phosphonic acids melamine salt is in flame retardant area
Application.
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| CN107903286B (en) * | 2017-10-17 | 2020-08-04 | 山东泰和水处理科技股份有限公司 | Fire retardant cyclohexylamine dimethylidene phosphonic acid and preparation method thereof |
Citations (9)
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