CN109651825A - A kind of metal ion complex fire retardant of containing phosphorus silicon nitrogen and the preparation method and application thereof - Google Patents
A kind of metal ion complex fire retardant of containing phosphorus silicon nitrogen and the preparation method and application thereof Download PDFInfo
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- CN109651825A CN109651825A CN201811473170.6A CN201811473170A CN109651825A CN 109651825 A CN109651825 A CN 109651825A CN 201811473170 A CN201811473170 A CN 201811473170A CN 109651825 A CN109651825 A CN 109651825A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
A kind of metal ion complex fire retardant of containing phosphorus silicon nitrogen and the preparation method and application thereof.The metal ion complex fire retardant of the containing phosphorus silicon nitrogen is that the ligand containing DOPO, POSS, catechol is successfully prepared by one-step method, again by itself and metallic ion coordination, the metal ion complex fire retardant (M (PDC) of containing phosphorus silicon nitrogen is synthesized1~3), with high thermal stability, there is good compatibility with epoxy resin, with strong catalytic action, can accelerate to generate a large amount of carbon residue in material combustion, generate fine and close layer of charcoal can play the role of it is heat-insulated oxygen-impermeable, to improve the flame retardant property of matrix.Metal ion complex (the M (PDC) of containing phosphorus silicon nitrogen1~3) in epoxy resin and curing agent solidification process, solidification temperature can be reduced, so that the metal ion complex of the containing phosphorus silicon nitrogen can also be as promotor when solidifying while being used as fire retardant.Metal ion complex (the M (PDC) of containing phosphorus silicon nitrogen1~3) be introduced in epoxy resin, substantially increase the mechanical performance of epoxy resin.
Description
Technical field
The present invention relates to metal ion complex fire retardants of a kind of containing phosphorus silicon nitrogen and the preparation method and application thereof, and belonging to has
Machine inorganic hybrid material field.
Background technique
Epoxy resin is as a member in numerous thermoset macromolecule materials, with mechanical strength is high, caking property is good, size
The advantages that stablizing height, resistance to acid and alkali, thus it is applied to every field.But the oxygen index (OI) of epoxy resin is only 19.8 or so, is belonged to
In combustible material, it is not able to satisfy the requirement in many fields.Therefore, novel effective fire retarding epoxide resin is developed to be concerned.
In order to promote the flame retardant property of material, the method being widely used at present is that fire retardant is added into epoxy resin.Phosphorus
System, silicon systems, nitrogenated flame retardant are gradually developed because meeting environmental requirement, wherein the polyhedral oligomeric sesquialter of cage structure
There is siloxanes (POSS) high thermal stability, DOPO and its derivative and epoxy resin to have good compatibility.Study table
Bright, the fire retardant simultaneously containing POSS and DOPO is evenly dispersed in polymeric matrix, and significantly improves polymeric matrix
Flame retardant property and mechanical performance.Many studies have shown that the flame retardant property of resin, metal can be improved in the introducing of certain metallic elements
There is element strong catalytic action matrix can be promoted to generate a large amount of carbon residue, while oxygen can be prevented to enter intrinsic silicon,
To improve the flame retardant property of matrix.But the metallic element introduced in the epoxy at present is usually inorganic salts, metal oxidation
The inorganic fillers such as object, bad with resin compatible, although it is introduced into matrix by mechanical blending, agglomeration is still bright
It is aobvious, it can significantly have lost the mechanical performance of matrix.The epoxy hardener of other high temperature class, solidification temperature when exclusive use
The high and time is long, generally requires the solidification for adding promotor catalyzed epoxies.Rarely have document report by being coordinated metal at present
Ion, POSS, DOPO are incorporated as the fire retardant of epoxy resin.
Summary of the invention
The purpose of the present invention is to provide metal ion complex fire retardants of a kind of containing phosphorus silicon nitrogen and preparation method thereof, and
The fire retardant is applied in epoxy resin.Metal ion complex fire retardant (the M (PDC) of containing phosphorus silicon nitrogen of the invention1~3) can
Be better dispersed in metal ion and POSS in epoxy resin by the method being simply mixed, improve the machinery of epoxy resin
Performance, the solidification temperature of epoxy resin and curing agent can be reduced by being introduced in epoxy-resin systems, make epoxy resin not
Normal cure in the case where promotor is needed, meanwhile, it can be cooperateed with when material combustion and play flame retardant effect.Wherein, silicon, phosphorus member
Element can promote the generation of layer of charcoal in combustion, and form SiO 2-ceramic layer in matrix surface, obstruct hot oxygen to base
Internal layer conduction, to prevent the further ablation of matrix；And metallic element meeting catalytic oxidative dehydrogenation under conditions of heated is anti-
It answers, accelerates the generation of layer of charcoal.The synergistic effect of silicon, phosphorus, three element of metal ion, substantially increases the anti-flammability of epoxy resin
Energy.
The technical solution adopted by the present invention to solve the technical problems first is that:
A kind of metal ion complex fire retardant of containing phosphorus silicon nitrogen, the metal ion complex fire retardant of the containing phosphorus silicon nitrogen
(M(PDC)1~3) it is shown in following molecular structural formula:
Wherein, M Cu2+、Fe3+、Zn2+Or Al3+Deng n is that 1~3, m is 1~3.
Wherein, R is non-reacted group, is isobutyl group, iso-octyl, ethyl, cyclohexyl, cyclopenta or phenyl etc.；X is
NO3 -Or CH3CH2COO-Deng.
The technical solution adopted by the present invention to solve the technical problems second is that:
A kind of preparation method of the metal ion complex fire retardant of above-mentioned containing phosphorus silicon nitrogen, the metal of the containing phosphorus silicon nitrogen
Ionic complex fire retardant is by amino oligomeric silsesquioxane (NH2- POSS), the miscellaneous -10- phospho hetero phenanthrene-of 9,10- dihydro-9-oxy
10- oxide (DOPO), 3,4- 4-dihydroxy benzaldehyde by ligand PDC of the one-step synthesis method containing catechol, then with metal
Ion carries out obtained by complexation reaction.The metal ion is Cu2+、Fe3+、Zn2+Or Al3+Deng.
The synthesis step of the metal ion complex fire retardant of the containing phosphorus silicon nitrogen specifically includes: by NH2-POSS、DOPO、
3,4- 4-dihydroxy benzaldehydes are dissolved with appropriate mixed solvent, lead to protective gas protection, be stirred at reflux at 50~65 DEG C reaction 8~
24h；After reaction, it precipitates, is separated by solid-liquid separation, solid portion is dried to obtain ligand PDC；By the ligand PDC and metal salinity
It is not dissolved in corresponding solvent, metal salt solution is slowly added dropwise into the solution dissolved with ligand, be slowly stirred 1 under room temperature
~4h, finally removes solvent for reaction solution, is washed with water and washs, and is separated by solid-liquid separation, and solid portion is dry, obtains the metal of containing phosphorus silicon nitrogen
Ionic complex fire retardant (M (PDC)1~3)。
In the reaction system of the metal ion complex fire retardant of the containing phosphorus silicon nitrogen, in molar ratio, NH2-POSS、
4-dihydroxy benzaldehyde=1:(1~1.2 DOPO, 3,4-): (1~1.2), ligand: metal ion=1:(1~3.2), the conjunction of ligand
The mixed solvent used in is by volume: chloroform (or methylene chloride): anhydrous methanol (or dehydrated alcohol)=(2~5): (1~
2), the soluble solvent of ligand: chloroform, methylene chloride etc., metal salt can dissolve solvent: dehydrated alcohol, anhydrous methanol etc..
The technical solution adopted by the present invention to solve the technical problems third is that:
A kind of modified fire retarding epoxide resin of metal ion complex fire retardant using above-mentioned containing phosphorus silicon nitrogen, described contains
The metal ion complex fire retardant of phosphorus silicon nitrogen is applied in epoxy resin, wherein the metal ion complex of containing phosphorus silicon nitrogen hinders
Fire 1~10wt% that agent dosage is fire retarding epoxide resin.
The epoxy resin is commodity epoxy resin, i.e., contains the compound of two or more epoxy groups in molecule, such as
Glycidol ether, glycidyl amine, ethylene oxidic ester etc.；Wherein glycidol ether has bisphenol A-type, bisphenol-f type and bisphenol S type
Deng；Glycidyl amine has aniline glycidyl amine, four glycidyl amine of diaminodiphenylmethane etc.；Ethylene oxidic ester has two shrinks
Glycerol is to (neighbour) phthalic acid ester etc..
The fire retarding epoxide resin further includes curing agent, and the epoxide equivalent of hardener dose and epoxy resin is stoichiometry
Than.The curing agent is the amine being used cooperatively with epoxy resin or anhydride compound etc., such as 4,4 '-diamino hexichol of amine
Methane, ethylenediamine, diethylenetriamine, m-phenylene diamine (MPD) etc.；Anhydride for example methyl tetrahydrophthalic anhydride, phthalic anhydride,
Pyromellitic dianhydride, methylcyclohexene tetracarboxylic anhydride etc..
The technical solution adopted by the present invention to solve the technical problems fourth is that:
The preparation method of the modified fire retarding epoxide resin of the metal ion complex fire retardant of the containing phosphorus silicon nitrogen, including with
Lower step:
(1) extracting epoxy resin is warming up to 55~100 DEG C, stirs 5~10min；
(2) metal ion network of the containing phosphorus silicon nitrogen dissolved with 1~5mL solvent is added into the epoxy resin of step 1)
Object fire retardant is closed, heats 55~100 DEG C, stirs 30~40min, removes solvent；
(3) curing agent is added, after mixing evenly, in 90~110 DEG C of 2~4h of heat preservation, continue 120~140 DEG C of heat preservations 1~
3h finally keeps the temperature 1~3h flame retardant epoxy modified to get the metal ion complex fire retardant of containing phosphorus silicon nitrogen at 150~160 DEG C
Resin.
The metal ion complex of containing phosphorus silicon nitrogen is made using the metal ion complex fire retardant of containing phosphorus silicon nitrogen by the present invention
Fire retarding epoxide resin.Its effect embodies as follows:
(1) present invention can prepare a variety of oligomeric silsesquioxane metal ions complexings by simple synthetic method
Object, synthetic method is simple, and applicability is extensive.
(2) metallic element, POSS, DOPO are uniformly dispersed in epoxy resin by the present invention by simply mixing, and are made
The flame retardant property for obtaining epoxy resin significantly improves, while can also improve the mechanical performance of epoxy resin.
(3) at high temperature, P elements promote the formation of layer of charcoal, form a protective layer in matrix surface, prevent matrix
Further ablation；And element silicon can matrix surface formed SiO 2-ceramic layer, prevent layer of charcoal thermal oxidative reaction and can
The gas release of combustion property；Metal ion after coordination is equivalent to an activation site, can be catalyzed POSS in heat effect and issue heat
Oxidation reaction makes it generate stable silicon oxide compound, while also P-O-C key can be promoted to degrade at a lower temperature, catalytic polymerization
Object forms stable protective layer at carbon, the effect of isolation heat and oxygen can be played, to improve the thermal stability of material.
(4) silicon phosphorus nitrogen metal ion synergistic acts on, and can substantially reduce content of the every kind of element in epoxy resin-base,
When adding the minimal amount of fire retardant in the epoxy, it will be able to play good flame retardant effect.It can reduce due to certain
One ignition-proof element content is relatively excessively high and causes to reduce the influence of epoxy resin-base performance.
(5) introducing metal ion can be solidified with catalyzed epoxies, thus greatly reduce epoxy resin and curing agent
Solidification temperature, can effectively save time and cost.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum of the iron ion complex compound fire retardant of containing phosphorus silicon nitrogen in embodiment 1.
Fig. 2 is the metal ion complex flame retardant epoxy tree of pure epoxy resin (a) and addition containing phosphorus silicon nitrogen in embodiment 1
DSC curve when promotor is not added when solidifying in rouge (b).
Fig. 3 be embodiment 1 epoxy resin in air by 600 DEG C processing after optical photograph.
Specific embodiment
Embodiment 1: when preparation R is isobutyl group, metal ions M Fe3+When, selected metal salt is Fe (NO3)3.9H2O, curing agent are methyl tetrahydrophthalic anhydride, and promotor is imidazoles, and synthesis condition is as follows, at this time m=3, n=3:
(1) synthesis of the iron ion complex compound fire retardant of containing phosphorus silicon nitrogen
By the NH of 8.75g2The 3,4- 4-dihydroxy benzaldehyde of-POSS, the DOPO of 2.60g and 1.66g, which are added to, is connected to condensation
In the 250mL three-necked flask of pipe, dissolved with the chloroform of 100mL and the anhydrous methanol mixed solution of 50mL, using N2It is protected,
12h is stirred at 55 DEG C.After reaction, it by reaction solution concentrated by rotary evaporation to about 25mL, is slowly dropped in ice methanol, precipitates,
Decompression filters.Repeatedly three times with ice methanol extraction, it is finally dried in vacuo and obtains ligand PDC for 24 hours.By the above-mentioned ligand of 10.90g
Fe (the NO of PDC and 1.21g3)3.9H2O is dissolved separately in chloroform and dehydrated alcohol, by Fe (NO3)3Solution is slowly added dropwise to molten
In the chloroformic solution for having ligand PDC, it is slowly stirred 2h under room temperature, obtains the solution of black, reaction solution is rotated to dry, then with steaming
Distilled water washing, ultrasound, decompression filter.It is washed with distilled water three times, is finally dried in vacuo the iron ion network for obtaining containing phosphorus silicon nitrogen for 24 hours
Close object fire retardant.The hydrogen nuclear magnetic resonance spectrogram of the iron ion complex compound fire retardant of the containing phosphorus silicon nitrogen is as shown in Figure 1, occur opposite
Answer group characteristic peak.
(2) preparation of the modified fire retarding epoxide resin of the iron ion complex compound fire retardant of containing phosphorus silicon nitrogen
The epoxy resin E-51 of 15g is added in 50mL single port bottle by (2-1), is heated to 55 DEG C, it is slowly stirred 5~
10min；
The iron ion complex compound fire retardant of the containing phosphorus silicon nitrogen of different content is dissolved in the methylene chloride of 1~5mL by (2-2)
(by mass percentage, the iron ion complex compound fire retardant of containing phosphorus silicon nitrogen is that the iron ion complex compound fire retardant of containing phosphorus silicon nitrogen is modified
Fire retarding epoxide resin 1%, 2%, 3%, 4%, the fire retarding epoxide resin of obtained modification is respectively designated as EP-1, EP-2,
EP-3, EP-4), it is slowly dropped in above-mentioned epoxy resin E-51, after being stirred until homogeneous, heats 55 DEG C, stir 30~40min,
Vacuumize removing dichloromethane solution；
The curing agent methyl tetrahydrophthalic anhydride of 13g is then added in (2-3), continues to be slowly stirred to uniform, addition
The imidazoles of 0.0028g is as promotor；It finally pours the mixture into in 100 DEG C of preheated stainless steel moulds, passes through journey
Sequence elevated cure is 100 DEG C of heating 2h, 120 DEG C of heating 3h, 160 DEG C of heating 1h respectively；Molding obtain the iron of containing phosphorus silicon nitrogen from
The modified fire retarding epoxide resin of sub- complex compound fire retardant.
(4) preparation of pure epoxy resin
Prepare one group of pure epoxy resin as a control group, specifically: the epoxy resin E-51 for weighing 15g is warming up to 55 DEG C,
The methyl tetrahydrophthalic anhydride of 13g is added, adds the imidazoles of 0.0028g as promotor, pours into mould after mixing evenly
Tool, is 100 DEG C of heating 2h, 120 DEG C of heating 3h, 160 DEG C of heating 1h respectively.Pure epoxy resin is obtained, EP-0 is named as.
(5) gained sample is tested into its oxygen index (OI) according to GB/T 2406.2-2009 method, and 3 points is carried out to each sample
As a result as shown in Table 1 and Table 2 crooked test illustrates that the iron ion complex compound fire retardant of the containing phosphorus silicon nitrogen of the present embodiment can be effective
Improve the flame retardant property and mechanical performance of modified epoxy.
The epoxy resin limiting oxygen index determination result of 1 embodiment 1 of table
| Test | EP-0 | EP-1 | EP-2 | EP-3 | EP-4 |
| Oxygen index (OI) (LOI) | 19.5 | 25.5 | 28.7 | 32.6 | 33.5 |
The epoxy resin three-point bend test result of 2 embodiment 1 of table
(6) referring additionally to above-mentioned steps but promotor imidazoles is not added, prepares corresponding pure epoxy resin (a) and containing phosphorus silicon nitrogen
Iron ion complex compound fire retarding epoxide resin (b), and both detect DSC curve in the case where promotor is not added when solidifying,
As shown in fig. 2, it can be seen that just there is curing agent methyl four in the case where no promotor, at about 245 DEG C in pure epoxy resin
The curing reaction exothermic phenomenon of hydrogen phthalic anhydride and epoxy resin, and observe that pure epoxy resin can not be solidified into when promotor is not added
Type.And when the iron ion complex compound fire retardant of containing phosphorus silicon nitrogen is added, the initial cure temperature of epoxy-resin systems is only 205
DEG C, there is exothermic maximum peak at about 260 DEG C, compared to pure epoxy resin system, solidification temperature is reduced obviously, and observes not
When adding promotor, also curable molding, explanation contain the modified fire retarding epoxide resin of the iron ion complex compound fire retardant of containing phosphorus silicon nitrogen
The solidification of the iron ion complex compound fire retardant of phosphorus silicon nitrogen being added with conducive to epoxy resin, can also work as while as fire retardant
Make promotor when solidifying.
Fig. 3 is each group epoxy resin -0, EP-1, and EP-2, EP-3, EP-4 is in air after 600 DEG C of processing
Optical photograph, it can be seen that pure epoxy EP-0 expulsion events occurs after 600 DEG C of processing, and becomes loose sheet, and EP-
1, original bulk morphologies are still maintain after EP-2, EP-3, EP-4 are thermally treated.This is because iron complex Fe (PDC)3
Middle POSS primitive is thermally generated silicon dioxide layer, and DOPO unit is heated also to will become continuous pyrophosphoric acid layer, while Fe3+Catalysis is poly-
Object is closed into carbon, in being ultimately formed fine and close protective layer, the small molecule that it not only can effectively prevent polymer cracking from generating is overflow
Out, moreover it is possible to well inside blocking oxygen and heat transfer to resin, to promote the flame retardant property of composite material.
Embodiment 2: when preparation R is isobutyl group, metal ions M Cu2+When, selected metal salt Cu (CH3CH2COO)2,
Its synthesis condition is as follows, at this point, m=2, n=2:
(1) synthesis of the copper ion complex compound fire retardant of containing phosphorus silicon nitrogen
By the NH of 8.75g2The 3,4- 4-dihydroxy benzaldehyde of-POSS, the DOPO of 2.60g and 1.66g, which are added to, is connected to condensation
In the 250mL three-necked flask of pipe, dissolved with the chloroform of 100mL and the dehydrated alcohol mixed solution of 50mL, using N2It is protected,
12h is stirred at 55 DEG C.After reaction, it by reaction solution concentrated by rotary evaporation to about 25ml, is slowly dropped in ice methanol, precipitates,
Decompression filters.Repeatedly three times with ice methanol extraction, it is finally dried in vacuo and obtains ligand PDC for 24 hours.By the above-mentioned ligand PDC of 9.69g
With the Cu (CH of 0.73g3CH2COO)2It is dissolved separately in chloroform and dehydrated alcohol, by Cu (CH3CH2COO)2Solution is slowly added dropwise
To dissolved in the chloroformic solution of ligand PDC, it is slowly stirred 2h under room temperature, obtains the solution of brown, reaction solution is rotated to dry, then
It is washed with distilled water, ultrasound, decompression filters.Be washed with distilled water three times, be finally dried in vacuo obtain for 24 hours the copper of containing phosphorus silicon nitrogen from
Sub- complex compound fire retardant.
(2) preparation of the modified fire retarding epoxide resin of the copper ion complex compound fire retardant of containing phosphorus silicon nitrogen
The epoxy resin E-51 of 15g is added in 50mL single port bottle by (2-1), is heated to 55 DEG C, it is slowly stirred 5~
10min；
The copper ion complex compound fire retardant of the containing phosphorus silicon nitrogen of different content is dissolved in the methylene chloride of 1~5mL by (2-2)
(by mass percentage, the copper ion complex compound fire retardant of containing phosphorus silicon nitrogen is that the copper ion complex compound fire retardant of containing phosphorus silicon nitrogen is modified
Fire retarding epoxide resin 1%, 2%, 3%, 4%, the fire retarding epoxide resin of obtained modification is respectively designated as EP-5, EP-6,
EP-7, EP-8), it is slowly dropped in above-mentioned epoxy resin E-51, after being stirred until homogeneous, vacuumizes removing dichloromethane solution；
The curing agent methyl tetrahydrophthalic anhydride of 13g is then added in (2-3), continues to be slowly stirred to uniform, addition
The imidazoles of 0.0028g is as promotor.It finally pours the mixture into in 100 DEG C of preheated stainless steel moulds, passes through journey
Sequence elevated cure is 100 DEG C of heating 2h, 120 DEG C of heating 3h, 160 DEG C of heating 1h respectively；Molding obtain the copper of containing phosphorus silicon nitrogen from
The modified fire retarding epoxide resin of sub- complex compound fire retardant.
(3) preparation of pure epoxy resin
Prepare one group of pure epoxy resin as a control group, specifically: the epoxy resin E-51 for weighing 15g is warming up to 55 DEG C,
The methyl tetrahydrophthalic anhydride of 13g is added, adds the imidazoles of 0.0028g as promotor, pours into mould after mixing evenly
Tool, is 100 DEG C of heating 2h, 120 DEG C of heating 3h, 160 DEG C of heating 1h respectively.Obtain pure epoxy resin EP-0.
(4) gained sample is tested into its oxygen index (OI) according to GB/T 2406.2-2009 method, as the result is shown the present embodiment
The copper ion complex compound fire retardant of containing phosphorus silicon nitrogen can effectively improve the flame retardant property of modified epoxy.
| Test | EP-0 | EP-5 | EP-6 | EP-7 | EP-8 |
| Oxygen index (OI) (LOI) | 19.5 | 24.9 | 26.2 | 29.5 | 30.6 |
Embodiment 3~8
With embodiment 1,2 techniques, change the type of metal salt in (2), calculate feed ratio, when metal salt is Fe
(CH3CH2COO)3、Al(CH3CH2COO)3、Al(NO3)3When, m=3, n=3；When metal salt is Zn (CH3CH2COO)2、Cu
(NO3)2When, m=2, n=2.
The above is only the preferred embodiment of the present invention, the range implemented of the present invention that therefore, it cannot be limited according to, i.e., according to
Equivalent changes and modifications made by the invention patent range and description, should still be within the scope of the present invention.
Claims (10)
1. a kind of metal ion complex fire retardant of containing phosphorus silicon nitrogen, it is characterised in that: the metal ion network of the containing phosphorus silicon nitrogen
Object fire retardant is closed to be shown below:
Wherein, M Cu2+、Fe3+、Zn2+Or Al3+；N is that 1~3, m is 1~3.
2. the metal ion complex fire retardant of containing phosphorus silicon nitrogen according to claim 1, it is characterised in that: the R is different
Butyl, iso-octyl, ethyl, cyclohexyl, cyclopenta or phenyl；The X is NO3 -Or CH3CH2COO-。
3. a kind of preparation method of the metal ion complex fire retardant of containing phosphorus silicon nitrogen described in claim 1, it is characterised in that:
By NH2- POSS, DOPO, 3,4- 4-dihydroxy benzaldehyde are dissolved with mixed solvent, under protective gas protection, are stirred at 50~65 DEG C
Mix back flow reaction 8~for 24 hours；After reaction, it precipitates, is separated by solid-liquid separation, solid portion is dried to obtain ligand；By the ligand and gold
Belong to salt to be dissolved separately in corresponding solvent, metal salt solution is added dropwise in ligand solution, after stirring 1~4h under room temperature,
Reaction solution removes solvent, washes, and is separated by solid-liquid separation, and the metal ion complex that solid portion is dried to obtain the containing phosphorus silicon nitrogen is fire-retardant
Agent.
4. the preparation method of the metal ion complex fire retardant of containing phosphorus silicon nitrogen according to claim 3, it is characterised in that:
In the reaction system of the metal ion complex fire retardant of the containing phosphorus silicon nitrogen, NH2- POSS, DOPO, 3,4- 4-dihydroxy benzaldehyde
Molar ratio be 1:1~1.2:1~1.2；The molar ratio of metal ion in the ligand and metal salt is 1:1~3.2.
5. the preparation method of the metal ion complex fire retardant of containing phosphorus silicon nitrogen according to claim 3, it is characterised in that:
The mixed solvent is the chloroform of volume ratio 2~5:1~2 or the mixed liquor of methylene chloride and anhydrous methanol or dehydrated alcohol；Institute
The solvent for stating corresponding ligand is chloroform or methylene chloride；The solvent of the corresponding metal salt is dehydrated alcohol or anhydrous methanol.
6. a kind of modified flame retardant epoxy tree of metal ion complex fire retardant using containing phosphorus silicon nitrogen described in claim 1
Rouge, it is characterised in that: the metal ion complex amount of flame-retardant agent of the containing phosphorus silicon nitrogen be fire retarding epoxide resin 1~
10wt%.
7. fire retarding epoxide resin according to claim 6, it is characterised in that: the epoxy resin is glycidol ether, contracting
Water glyceramine or ethylene oxidic ester.
8. fire retarding epoxide resin according to claim 7, it is characterised in that: the glycidol ether is bisphenol A-type, bis-phenol
F type or bisphenol S type；The glycidyl amine is four glycidyl amine of aniline glycidyl amine or diaminodiphenylmethane；It is described
Ethylene oxidic ester is 2-glycidyl terephthalate or 2-glycidyl phthalic acid ester.
9. fire retarding epoxide resin according to claim 6, it is characterised in that: the fire retarding epoxide resin further includes solidification
Agent, the curing agent are amine or anhydride compound；The amine is 4,4 '-diaminodiphenylmethane, ethylenediamine, divinyl
Triamine or m-phenylene diamine (MPD)；The anhydride is methyl tetrahydrophthalic anhydride, phthalic anhydride, pyromellitic dianhydride or first
Cyclohexene tetracarboxylic anhydride.
10. a kind of preparation method of fire retarding epoxide resin as claimed in claim 6, it is characterised in that: include:
1) extracting epoxy resin is warming up to 55~100 DEG C, stirs 5~10min；
2) metal ion complex of the containing phosphorus silicon nitrogen dissolved with 1~5mL solvent is added into the epoxy resin of step 1)
Fire retardant heats 55~100 DEG C, stirs 30~40min, removes solvent；
3) curing agent is added, after mixing evenly, in 90~110 DEG C of 2~4h of heat preservation, continues in 120~140 DEG C of 1~3h of heat preservation, most
1~3h fire-retardant ring modified to get the metal ion complex fire retardant of the containing phosphorus silicon nitrogen is kept the temperature at 150~160 DEG C afterwards
Oxygen resin.
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| CN201811473170.6A CN109651825B (en) | 2018-12-04 | 2018-12-04 | Phosphorus-silicon-nitrogen-containing metal ion complex flame retardant and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110655652A (en) * | 2019-09-02 | 2020-01-07 | 厦门大学 | Metal hybrid POSS flame retardant, preparation method and application |
| CN112662269A (en) * | 2020-11-20 | 2021-04-16 | 陈冬芬 | Flame-retardant epoxy floor coating and preparation method thereof |
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| CN110655652A (en) * | 2019-09-02 | 2020-01-07 | 厦门大学 | Metal hybrid POSS flame retardant, preparation method and application |
| CN114364729A (en) * | 2019-09-11 | 2022-04-15 | 科莱恩国际有限公司 | Flame retardant composition, polymer molding composition containing the same and use thereof |
| CN114364729B (en) * | 2019-09-11 | 2023-09-29 | 科莱恩国际有限公司 | Flame retardant composition, polymer molding composition comprising the same and use thereof |
| CN112662269A (en) * | 2020-11-20 | 2021-04-16 | 陈冬芬 | Flame-retardant epoxy floor coating and preparation method thereof |
| CN112920552A (en) * | 2021-01-27 | 2021-06-08 | 江苏扬农化工集团有限公司 | Flame-retardant epoxy resin and preparation method and application thereof |
| CN114437661A (en) * | 2021-12-21 | 2022-05-06 | 江苏集萃先进高分子材料研究所有限公司 | High-temperature-resistant composite modified waterborne polyurethane adhesive and preparation method thereof |
| CN114957794A (en) * | 2022-06-01 | 2022-08-30 | 山东甲子湖畔新材料科技有限公司 | Halogen-free flame retardant and preparation method thereof |
| CN115256576A (en) * | 2022-06-23 | 2022-11-01 | 德华兔宝宝装饰新材股份有限公司 | Method for treating wood veneer, wood veneer and anti-rust flame-retardant plywood |
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