CN106243385A - A kind of DOPO based flameproofing and preparation method thereof - Google Patents
A kind of DOPO based flameproofing and preparation method thereof Download PDFInfo
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- CN106243385A CN106243385A CN201610606516.XA CN201610606516A CN106243385A CN 106243385 A CN106243385 A CN 106243385A CN 201610606516 A CN201610606516 A CN 201610606516A CN 106243385 A CN106243385 A CN 106243385A
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- 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
- C08K5/5333—Esters of phosphonic acids
- C08K5/5373—Esters of phosphonic acids containing heterocyclic rings not representing cyclic esters of phosphonic acids
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- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65744—Esters of oxyacids of phosphorus condensed with carbocyclic or heterocyclic rings or ring systems
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- 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
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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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
The invention discloses a kind of DOPO based flameproofing and preparation method thereof.The method is with 9, and 10 dihydro 9 oxa-10 phospho hetero phenanthrene 10 oxides and paraformaldehyde are raw material, synthesize presoma by substitution reaction.The active hydroxyl groups utilized, then itself and PhosphorodichloridicAcid Acid Phenyl Ester, 2-(Acryloyloxy)ethanol are replaced/esterification prepares phosphorus content height and carries the fire retardant of activity double key.This fire-retardant is applied in unsaturated polyester resin matrix, forms flame-retarded unsaturated polyester resin composite.The fire retardant of the present invention can improve the fire resistance of unsaturated-resin matrix material by gas phase and condensed phase, overcomes the shortcomings such as existing additive flame retardant is low with polymeric matrix poor compatibility, easily migration and flame retarding efficiency.This fire retardant is when flame-retarded unsaturated polyester resin, and under relatively low addition, the vertical combustion grade of material can reach V 0 rank, good flame retardation effect.Product purity of the present invention is high, productivity is high, post processing is easy.
Description
Technical field
The invention belongs to fire retardant design and preparing technical field, be specifically related to a kind of DOPO based flameproofing and preparation side thereof
Method.
Background technology
Macromolecular material is owing to having much excellent performance such as chemical stability processing good, easy, low cost etc., at present
Have been widely used for the numerous areas such as electronic communication, biological medicine, Aero-Space, auto industry, building.But, great majority
Macromolecular material at high temperature easily decomposition combustion, release amount of heat and toxic gas, jeopardize human life and wealth simultaneously
Produce safety.In order to give full play to these polymeric materials potentiality in industrial application, improving that its fire resistance becomes must
The act wanted.The most widely used in each base polymer add fire retardant to improve its fire resistance, containing phosphorous fire retardant due to
Possess the advantages such as " environmentally friendly " and highly effective flame-retardant, cause the extensive concern of lot of domestic and foreign scholar.
9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxide (DOPO) is as in a kind of novel environment friendly fire retardant
Mesosome, due in its molecular structure containing cyclohexyl biphenyl and phenanthrene ring structure, simultaneously possibly together with active phosphorus-hydrogen bond, can with olefin-containing,
Epoxy bond and carbonyl compound reaction generate the derivant of unique properties.But the degradation temperature of DOPO and derivant thereof compares
Low, poor heat stability, easily it is heated in high temperature process and melted degraded, it is impossible to meet the processing temperature of most polymer material
Degree.
It is solid that China Patent Publication No. CN104086751A reports a kind of DOPO base s-triazine hydrogenated benzimidazole epoxy
Agent and preparation method thereof.First intermediate compound I 2,4,6-tri-(4-aldehyde radical is obtained with Cyanuric Chloride, hydroxy benzaldehyde for raw material
Phenoxy group)-1,3,5-s-triazine ring；Then intermediate compound I is reacted with DOPO and obtain intermediate II DOPO base 2,4,6-tri-(4-aldehyde
Phenoxyl)-1,3,5-s-triazine ring；Finally intermediate II and o-phenylenediamine are reacted and obtain final fire retardant DOPO base equal three
Piperazine hydrogenated benzimidazole epoxy hardener, the vertical combustion grade of this firming agent passes through UL-94V-0 level, good flame retardation effect.But
Must use catalyst in the preparation process of this fire retardant, the pollution to environment is bigger.
China Patent Publication No. CN103881134A reports a kind of DOPO and derives phosphor nitrogen combustion inhibitor and preparation method thereof.?
Under the conditions of solution backflow azeotropic water removing, N hydroxymethyl acrylamide solution is added drop-wise in DOPO solution, can synthesize and obtain mesh
Mark product DOPO-HAM, this fire retardant has the advantages such as heat stability is high, phosphorus nitrogen cooperative flame retardant is effective.But while reacted
Journey uses azeotropic water removing method, can not avoid DOPO that the reaction of part hydrolysis occurs completely, and then cause not react completely
Entirely.And in the flame retardant test of Cotton Gossypii, when phosphorous mass fraction is 1.09% in cotton, also can only achieve UL-94V-1 rank.
China Patent Publication No. 104193967A reports a kind of bisphenol-A-mono-benzimidazole dihydrochloride/epoxy resin containing double DOPO
Copolymer.First the intermediate compound I bisphenol-A containing double DOPO is prepared for raw material, in inciting somebody to action afterwards with DOPO and bisphenol-A-bis-benzimidazole dihydrochlorides
Mesosome I and aniline, polyformaldehyde reaction obtain fire retardant bisphenol-A-mono-benzimidazole dihydrochloride containing double DOPO.By prepared fire retardant with
Epoxy resin obtains fire proofing after being mixed in proportion intensification ring opening copolymer.But this is fire-retardant when 50wt% for fire retardant addition
Material can be only achieved V-0 rank, and fire retardant addition is bigger.
Above as a example by DOPO based flameproofing, fire retardant application present situation in macromolecular material is briefly described
And anatomy, it is indicated that the problems that there is also in fire retardant application.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of DOPO based flameproofing, this fire retardant is a kind of
Response type phosphor-containing halogen-free DOPO based flameproofing, multiple containing unsaturation when being applied to epoxy acrylic resin, unsaturated-resin etc.
The fire resistance of material can be significantly improved time in the polymeric matrix of double bond.
Another object of the present invention provides the above-mentioned easy preparation method of DOPO based flameproofing.
For solving above technical problem, the present invention takes techniques below scheme.
A kind of DOPO based flameproofing, this fire retardant outward appearance is clear yellow viscous type liquid, described fire retardant particular chemical
As follows, comprise three parts, a part removes hydroxylic moiety for the modified monohydric alcohol of DOPO base, has the fire-retardant effectiveness of gas phase；
A part is the phosphoric acid ester part of phosphorus element-containing, has condensed phase fire retardation；Another part is then active double bond
2-(Acryloyloxy)ethanol class part.
Wherein, R1For methyl, methoxyl group, ethyl, ethyoxyl, phenyl or phenoxy group；R2For H atom or methyl.
Preferably, R1For methyl, methoxyl group, phenyl or phenoxy group.
The preparation method of the above a kind of DOPO based flameproofing, the method with 9,10-dihydro-9-oxy miscellaneous-10-phospha
Phenanthrene-10-oxide (DOPO) and paraformaldehyde are raw material, synthesize phosphorus-containing compound presoma I by substitution reaction.Before utilization
Drive the active hydroxyl groups of body I, then itself and phosphinylidyne dichloro, acrylate hydroxyl ethyl ester class are replaced/esterification prepares height and contains
The reaction-type flame-retarding monomer II of phosphorus amount and activity double key, concrete preparation process is as follows:
(1) it is first according to react mol ratio be dissolved in by DOPO in solvent 1, under inert gas shielding, temperature is risen to instead
Temperature 1 is answered to react a period of time；Again paraformaldehyde is entered in reaction system after DOPO is completely dissolved, temperature is risen to reaction
Temperature 2 makes solution be in reflux state to keep this conditioned response a period of time；After question response completes, it is cooled to room temperature, filters, use
Solvent 1 washing precipitate；This precipitate is put in vacuum drying oven and be vacuum dried, heat pressurize a period of time；Afterwards, it is cooled to
Room temperature, obtains presoma I, and concrete synthetic route is as follows:
(2) phosphinylidyne dichloro is dissolved in solvent 2, stirring reaction a period of time under ice bath temperature；Press in reaction system
Certain mol proportion is slowly added to acid binding agent and the reaction of solvent 2 ice bath；Be slowly added dropwise afterwards acrylate hydroxyl ethyl ester compound and
Solvent 2 ice bath reacts 4～6 hours；Backward reaction system in be slowly added to presoma I and the mixture of solvent 2, ice bath reacts
Room temperature reaction 8～12 hours it are warming up to after 4～6 hours；After question response terminates, being filtered to remove acid binding agent salt, rotation is evaporated off the most anti-
Answering monomer and solvent, i.e. can get pure DOPO based flameproofing II, concrete synthetic route is as follows:
Preferably, the general structure of described phosphinylidyne dichloro is Cl2POR1,
It is further preferred that described phosphinylidyne dichloro be PhosphorodichloridicAcid Acid Phenyl Ester, diphenylphosphoryl dichloro, methyl phosphinylidyne dichloro,
One in methoxyl group phosphinylidyne dichloro, ethyl phosphinylidyne dichloro and ethyoxyl phosphinylidyne dichloro.
Preferably, described acrylate hydroxyl ethyl ester compound is in 2-(Acryloyloxy)ethanol and hydroxyethyl methylacrylate
A kind of.
Preferably, in step (1), described solvent 1 is selected from toluene or dimethylbenzene.
Preferably, in step (1), described noble gas is selected from nitrogen, helium or argon.
Preferably, in step (1), described reaction temperature 1 is 75～85 DEG C.
Preferably, in step (1), described reaction temperature 2 is 90～100 DEG C.
Preferably, in step (1), described reacting reflux time is 6～10 hours.
Preferably, in step (1), described washing uses toluene to wash 2～3 times.
Preferably, in step (1), described vacuum drying temperature is 60～80 DEG C, and the vacuum drying time is 8～12 hours.
Preferably, in step (1), described paraformaldehyde and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide etc.
Mol ratio.
Preferably, in step (2), described presoma I and acrylate hydroxyl ethyl ester compound equimolar ratio.
Preferably, in step (2), described solvent 2 is selected from oxolane, dichloromethane or chloroform.
Preferably, in step (2), described phosphoric acid dichloro is 1:(1～4 with the mol ratio of acid binding agent), described phosphinylidyne dichloro
It is 1:(1～2 with the mol ratio of acrylate hydroxyl ethyl ester compound).
Preferably, in step (2), described acid binding agent is triethylamine.
Preferably, in step (2), described ice bath temperature is-10～5 DEG C；
Preferably, in step (2), described room temperature is 25 DEG C.
Preferably, in step (2), it is 40～60 DEG C that temperature is steamed in described rotation.
One of purposes of obtained flame-retardant agent of the present invention, is i.e. to apply at unsaturated polyester resin (UPR) or epoxy acrylic
In resin (EA), improve anti-flammability.
Compared with prior art, present invention have the advantage that
The present invention synthesizes phosphorus-containing compound presoma I by substitution reaction.Utilize the active hydroxyl groups of I, then by itself and phosphorus
Acyl dichloro, 2-(Acryloyloxy)ethanol class replace/and esterification prepares the response type DOPO base of high phosphorus content and activity double key
Fire retardant II.The flame-retardant monomer molecular weight of the present invention is higher, can improve Flame Retardancy energy by gas phase and condensed phase, overcome
Existing little molecular phosphorus flame retardant heat decomposition temperature is low and polymeric matrix poor compatibility, easily migrate, flame retarding efficiency is low etc. lacks
Point.This fire retardant when flame-retarded unsaturated polyester resin under relatively low addition the vertical combustion grade of material can reach V-
0 rank, good flame retardation effect.Product purity of the present invention and productivity are higher, and last handling process is easy.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described in detail, but is not limited to these embodiments.
Number in following example, unless otherwise indicated, refers to parts by weight and percentage by weight.
Embodiment 1:
The first step, equipped with thermometer, nitrogen ingress pipe and reflux condenser (tail end with equipped with anhydrous calcium chloride drying tube
Be connected) 500mL there-necked flask in, add 0.5mol (108g) DOPO (9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxygen
Compound) and 200mL toluene, stirring is warming up to 80 DEG C under nitrogen protection, to be mixed be completely dissolved to DOPO after, add 15g's
Paraformaldehyde, then heats to 95 DEG C of back flow reaction 8h, can produce white precipitate in reaction.When stopped reaction after reaction completely,
Desciccate I is obtained by toluene filtration washing precipitation and at 70 DEG C of vacuum drying 10h.
Second step, PhosphorodichloridicAcid Acid Phenyl Ester (PDCP) (21.1g, 0.1mol) and 80mL oxolane (THF) add 250mL
It is furnished with in the there-necked flask of mechanical agitator, system temperature is controlled at 0 DEG C；In system, triethylamine is added after 30 minutes
(TEA) (21.3g, 0.21mol)；Instill 2-(Acryloyloxy)ethanol (HEA) (11.6g, 0.1mol) and 20mL THF, this process subsequently
Continue 2 hours；Question response adds product I (0.1mol, 24.6g) and 20mL oxolane after continuing 4 hours, and this process continues 2
Hour；Then system was warmed to room temperature reaction after 4 hours by reaction, and reaction is filtered to remove triethylamine salt after continuing 10 hours, 40 DEG C
Rotation steaming obtains end product clear yellow viscous type liquid D OPO based flameproofing II.Productivity 80%.
Product structure characterizes:
FTIR(KBr,cm-1):3071(ν=C-H),2961-2922(ν-C-H),1953(νbenzene),1730(νC=O),1638
(νC=C),1480-1405(δC-H),1280(νP=O),1200(νc-c),1080(νP-O).1H-NMR(400MHz,CDCl3-d,
ppm):7.95-7.01(m,13H),6.27(dd,1H),6.05(m,1H),5.59(t,1H),4.88(dd,2H),4.47(t,
2H),4.31(dd,2H)。
Embodiment 2
The first step, equipped with thermometer, nitrogen ingress pipe and reflux condenser (tail end with equipped with anhydrous calcium chloride drying tube
Be connected) 500mL there-necked flask in, add 0.5mol (108g) DOPO and 200mL toluene, under nitrogen protection stirring be warming up to
75 DEG C, to be mixed be completely dissolved to DOPO after, add 15g paraformaldehyde, then heat to 90 DEG C of back flow reaction 10h, reaction
In can produce white precipitate.When stopped reaction after reaction completely, obtain by toluene filtration washing precipitation and at 80 DEG C of vacuum drying 10h
To desciccate I.
Second step, PhosphorodichloridicAcid Acid Phenyl Ester (PDCP) (21.1g, 0.1mol) and 80mL dichloromethane add 250mL to be furnished with
In the there-necked flask of mechanical agitator, system temperature is controlled at-10 DEG C；In system, triethylamine (TEA) is added after 30 minutes
(21.3g, 0.21mol)；Instill hydroxyethyl methylacrylate (HEMA) (13.0g, 0.1mol) and 20mL oxolane subsequently, this
Process continues 2 hours；Question response adds product I (0.1mol, 24.6g) and 20mL oxolane after continuing 4 hours, and this process is held
Continuous 2 hours；Then system was warmed to room temperature reaction after 4 hours by reaction, and reaction is filtered to remove triethylamine salt after continuing 12 hours, and 40
DEG C rotation steaming obtain end product clear yellow viscous type liquid D OPO based flameproofing II.Productivity 82%.
Product structure characterizes:
FTIR(KBr,cm-1):3071(ν=C-H),2961-2922(ν-C-H),1953(νbenzene),1730(νC=O),1638
(νC=C),1480-1405(δC-H),1280(νP=O),1200(νc-c),1080(νP-O).1H-NMR(400MHz,CDCl3-d,
ppm):7.95-7.01(m,13H),6.48(d,1H),6.40(d,1H),4.88(t,2H),4.47(t,2H),4.31(dd,
2H),2.01(d,1H)。
Embodiment 3:
The first step, equipped with thermometer, nitrogen ingress pipe and reflux condenser (tail end with equipped with anhydrous calcium chloride drying tube
Be connected) 500mL there-necked flask in, add 0.5mol (108g) DOPO and 200mL toluene, under nitrogen protection stirring be warming up to
80 DEG C, to be mixed be completely dissolved to DOPO after, add 15g paraformaldehyde, then heat to 95 DEG C of back flow reaction 8h, in reaction
White precipitate can be produced.When stopped reaction after reaction completely, obtain by toluene filtration washing precipitation and at 70 DEG C of vacuum drying 12h
Desciccate I.
Second step, PhosphorodichloridicAcid Acid Phenyl Ester (PDCP) (21.1g, 0.1mol) and 80mL chloroform add 250mL and are furnished with machinery
In the there-necked flask of agitator, system temperature is controlled at 5 DEG C；After 30 minutes toward system adds triethylamine (TEA) (21.3g,
0.21mol)；Instilling 2-(Acryloyloxy)ethanol (HEA) (11.6g, 0.1mol) and 20mL chloroform subsequently, this process continues 2 hours；Treat
Reaction adds product I (0.1mol, 24.6g) and 20mL chloroform after continuing 3 hours, and this process continues 2 hours；Then reaction 5 is little
System was warmed to room temperature time after reaction, and reaction is filtered to remove triethylamine salt after continuing 10 hours, and 50 DEG C of rotation steamings obtain end product
Clear yellow viscous type liquid D OPO based flameproofing II.Productivity 78%.
Product structure characterizes:
FTIR(KBr,cm-1):3071(ν=C-H),2961-2922(ν-C-H),1953(νbenzene),1730(νC=O),1638
(νC=C),1480-1405(δC-H),1280(νP=O),1200(νc-c),1080(νP-O).1H-NMR(400MHz,CDCl3-d,
ppm):7.95-7.01(m,13H),6.27(dd,1H),6.05(m,1H),5.59(t,1H),4.88(dd,2H),4.47(t,
2H),4.31(dd,2H)。
Embodiment 4:
The first step, equipped with thermometer, nitrogen ingress pipe and reflux condenser (tail end with equipped with anhydrous calcium chloride drying tube
Be connected) 500mL there-necked flask in, add 0.5mol (108g) DOPO and 200mL toluene, under nitrogen protection stirring be warming up to
85 DEG C, to be mixed be completely dissolved to DOPO after, add 15g paraformaldehyde, then heat to 100 DEG C of back flow reaction 6h, reaction
In can produce white precipitate.When stopped reaction after reaction completely, obtain by toluene filtration washing precipitation and at 80 DEG C of vacuum drying 10h
To desciccate I.
Second step, diphenylphosphoryl dichloro (19.5g, 0.1mol) and 80mL oxolane (THF) add 250mL and are furnished with machinery
In the there-necked flask of agitator, system temperature is controlled at 0 DEG C；After 30 minutes toward system adds triethylamine (TEA) (21.3g,
0.21mol)；Instilling 2-(Acryloyloxy)ethanol (HEA) (11.6g, 0.1mol) and 20mL THF subsequently, this process continues 2 hours；Treat
Reaction adds product I (0.1mol, 24.6g) and 20mL oxolane after continuing 4 hours, and this process continues 2 hours；Then react
System was warmed to room temperature after 4 hours reaction, and reaction is filtered to remove triethylamine salt after continuing 10 hours, and 60 DEG C of rotation steamings are finally produced
Thing clear yellow viscous type liquid D OPO based flameproofing II.Productivity 80%.
Product structure characterizes:
FTIR(KBr,cm-1):3071(ν=C-H),2961-2922(ν-C-H),1953(νbenzene),1730(νC=O),1638
(νC=C),1480-1405(δC-H),1280(νP=O),1200(νc-c),1080(νP-O).1H-NMR(400MHz,CDCl3-d,
ppm):7.95-7.01(m,13H),6.27(dd,1H),6.05(m,1H),5.59(t,1H),4.88(dd,2H),4.47(t,
2H),4.31(dd,2H)。
Embodiment 5:
The first step, equipped with thermometer, nitrogen ingress pipe and reflux condenser (tail end with equipped with anhydrous calcium chloride drying tube
Be connected) 500mL there-necked flask in, add 0.5mol (108g) DOPO and 200mL toluene, under nitrogen protection stirring be warming up to
75 DEG C, to be mixed be completely dissolved to DOPO after, add 15g paraformaldehyde, then heat to 90 DEG C of back flow reaction 10h, reaction
In can produce white precipitate.When stopped reaction after reaction completely, obtain by toluene filtration washing precipitation and at 60 DEG C of vacuum drying 12h
To desciccate I.
Second step, diphenylphosphoryl dichloro (19.5g, 0.1mol) and 80mL oxolane (THF) add 250mL and are furnished with machinery
In the there-necked flask of agitator, system temperature is controlled at 0 DEG C；After 30 minutes toward system adds triethylamine (TEA) (21.3g,
0.21mol)；Instilling hydroxyethyl methylacrylate (HEMA) (13.0g, 0.1mol) and 20mL THF subsequently, it is little that this process continues 2
Time；Question response adds product I (0.1mol, 24.6g) and 20mL oxolane after continuing 4 hours, and this process continues 2 hours；Connect
After reaction 4 hours, system being warmed to room temperature reaction, reaction is filtered to remove triethylamine salt after continuing 10 hours, and 40 DEG C of rotation steamings obtain
End product clear yellow viscous type liquid D OPO based flameproofing II.Productivity 80%.
Product structure characterizes:
FTIR(KBr,cm-1):3071(ν=C-H),2961-2922(ν-C-H),1953(νbenzene),1730(νC=O),1638
(νC=C),1480-1405(δC-H),1280(νP=O),1200(νc-c),1080(νP-O).1H-NMR(400MHz,CDCl3-d,
ppm):7.95-7.01(m,13H),6.48(d,1H),6.40(d,1H),4.88(t,2H),4.47(t,2H),4.31(dd,
2H),2.01(d,1H)。
Embodiment 6:
The first step, equipped with thermometer, nitrogen ingress pipe and reflux condenser (tail end with equipped with anhydrous calcium chloride drying tube
Be connected) 500mL there-necked flask in, add 0.5mol (108g) DOPO and 200mL toluene, under nitrogen protection stirring be warming up to
80 DEG C, to be mixed be completely dissolved to DOPO after, add 15g paraformaldehyde, then heat to 95 DEG C of back flow reaction 10h, reaction
In can produce white precipitate.When stopped reaction after reaction completely, obtain by toluene filtration washing precipitation and at 80 DEG C of vacuum drying 8h
To desciccate I.
Second step, methyl phosphinylidyne dichloro (13.2g, 0.1mol) and 80mL oxolane (THF) add 250mL and are furnished with machinery
In the there-necked flask of agitator, system temperature is controlled at 0 DEG C；After 30 minutes toward system adds triethylamine (TEA) (21.3g,
0.21mol)；Instilling 2-(Acryloyloxy)ethanol (HEA) (11.6g, 0.1mol) and 20mL THF subsequently, this process continues 2 hours；Treat
Reaction adds product I (0.1mol, 24.6g) and 20mL oxolane after continuing 6 hours, and this process continues 2 hours；Then react
System was warmed to room temperature after 6 hours reaction, and reaction is filtered to remove triethylamine salt after continuing 12 hours, and 40 DEG C of rotation steamings are finally produced
Thing clear yellow viscous type liquid D OPO based flameproofing II.Productivity 73%.
Product structure characterizes:
FTIR(KBr,cm-1):3071(ν=C-H),2961-2922(ν-C-H),1953(νbenzene),1730(νC=O),1638
(νC=C),1480-1405(δC-H),1280(νP=O),1200(νc-c),1080(νP-O).1H-NMR(400MHz,CDCl3-d,
ppm):7.95-7.01(m,8H),6.27(dd,1H),6.05(m,1H),5.59(t,1H),4.88(dd,2H),4.47(t,
2H),4.31(dd,2H),1.43(d,3H)。
Embodiment 7:
In order to investigate the fire retardation of the DOPO base response type phosphor-containing halogen-free fire retardant II of the present invention, the present embodiment selects one
Kind inflammable unsaturated polyester resin (UPR) as matrix, by embodiment 1-6 prepares fire retardant formula as below (see
Table 1) join in UPR, it is poured into after mix homogeneously in mould, after 90 DEG C of solidification 24h, standard specimen is prepared in cold curing.Right
These standard specimens carry out fire resistance (UL94 reference standard: ASTM D3801-10；LOI reference standard: ASTM D2863-
06A), its test result is shown in Table 1.
Table 1
As shown in Table 1, when fire retardant addition is more than or equal to 20wt%, the fire resistance of unsaturated polyester resin is relatively
Good, V-0 rank can be reached, limited oxygen index reaches 34%.
Embodiment 8:
In order to investigate the DOPO based flameproofing II of the present invention fire retardation in epoxy acrylic resin, the present embodiment selects
With a kind of inflammable epoxy acrylic resin (EA) as matrix, fire retardant II embodiment 1-6 prepared is according to formula as below
(being shown in Table 2) joins in EA, is poured in mould after mix homogeneously, prepares standard specimen by UV solidification.To these standards
Sample carries out fire resistance (UL94 reference standard: ASTM D3801-10；LOI reference standard: ASTM D2863-06A), it is surveyed
Test result is shown in Table 2.
Table 2
As shown in Table 2, when retardant load level is more than or equal to 25wt%, the fire resistance of epoxy acrylic resin is preferable,
Can reach V-0 rank, limited oxygen index reaches 32%.
As can be seen from the above embodiments, the present invention prepares DOPO base phosphorous response type halogen-free flame retardants reaction condition easily in fact
Existing, simple to operate, the anti-flammability containing unsaturated double-bond resin such as unsaturated polyester (UP), epoxy acrylic can be significantly improved simultaneously
Energy.
Above the present invention is described in detail, its object is to allow the personage being familiar with this art will appreciate that this
Invention content and be carried out, can not limit the scope of the invention with this, all spirit institutes according to the present invention
The equivalence change made or modification, all should contain within the scope of the present invention.
Claims (10)
1. a DOPO based flameproofing, it is characterised in that this fire retardant is clear yellow viscous type liquid, comprises three parts, a part
Remove hydroxylic moiety for the modified monohydric alcohol of DOPO base, there is the fire-retardant effectiveness of gas phase；A part is the phosphoric acid ester of phosphorus element-containing
Part, has condensed phase fire retardation；Another part is then the 2-(Acryloyloxy)ethanol class part of active double bond, described fire-retardant
The chemical constitution of agent is as follows:
Wherein, R1For methyl, methoxyl group, ethyl, ethyoxyl, phenyl or phenoxy group；R2For H atom or methyl.
2. the method for the preparation a kind of DOPO based flameproofing described in claim 1, it is characterised in that the method with 9,10-dihydro-
9-oxa--10-phospho hetero phenanthrene-10-oxide and paraformaldehyde are raw material, synthesize phosphorus-containing compound presoma by substitution reaction
Active hydroxyl groups and phosphinylidyne dichloro, the acrylate hydroxyl ethyl ester compound of I, recycling presoma I replace/esterification system
For going out the phosphorous response type DOPO based flameproofing II with activity double key, concrete preparation process is as follows:
(1) first 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dissolved in solvent 1, in inert gas shielding
Lower temperature is risen to reaction temperature 1；To be many again after 9,10-dihydro-9-oxy miscellaneous-10-phospho hetero phenanthrene-10-oxide is completely dissolved
Polyformaldehyde is put in reaction system, temperature rises to reaction temperature 2 and makes solution be in reflux state；After question response completes, cooling
To room temperature, filter, with solvent 1 washing precipitate；This precipitate is put in vacuum drying oven and be vacuum dried；Afterwards, it is cooled to room
Temperature, obtains presoma I, and concrete synthetic route is as follows:
(2) phosphinylidyne dichloro is dissolved in solvent 2, stirs under ice bath；Add the reaction of acid binding agent ice bath；Drip acrylic acid afterwards
Ester hydroxyl ethyl ester compound and solvent 2 ice bath react 4～6 hours；Adding presoma I and the mixture of solvent 2 afterwards, ice bath is anti-
Reaction 8～12 hours it is warmed to room temperature after answering 4～6 hours；After question response terminates, being filtered to remove acid binding agent salt, rotation is evaporated off the most anti-
Answering monomer and solvent, i.e. can get pure DOPO based flameproofing II, concrete synthetic route is as follows:
The preparation method of a kind of DOPO based flameproofing the most according to claim 2, it is characterised in that: described phosphinylidyne dichloro
General structure is Cl2POR1。
The preparation method of a kind of DOPO based flameproofing the most according to claim 2, it is characterised in that: described phosphinylidyne dichloro is
PhosphorodichloridicAcid Acid Phenyl Ester, diphenylphosphoryl dichloro, methyl phosphinylidyne dichloro, methoxyl group phosphinylidyne dichloro, ethyl phosphinylidyne dichloro and ethyoxyl
One in phosphinylidyne dichloro；Described acrylate hydroxyl ethyl ester compound is in 2-(Acryloyloxy)ethanol and hydroxyethyl methylacrylate
One.
The preparation method of a kind of DOPO based flameproofing the most according to claim 2, it is characterised in that: in step (1), described
Solvent 1 is toluene or dimethylbenzene；Described noble gas is nitrogen, helium or argon.
The preparation method of a kind of DOPO based flameproofing the most according to claim 2, it is characterised in that: in step (1), described
Reaction temperature 1 is 75～85 DEG C；Described reaction temperature 2 is 90～100 DEG C；The time of described backflow is 6～10 hours；Described wash
Wash employing toluene to wash 2～3 times；Described vacuum drying temperature is 60～80 DEG C, and the vacuum drying time is 8～12h.
The preparation method of a kind of DOPO based flameproofing the most according to claim 2, it is characterised in that: in step (1), described
Paraformaldehyde-10-miscellaneous with 9,10-dihydro-9-oxy phospho hetero phenanthrene-10-oxide equimolar ratio.
The preparation method of a kind of DOPO based flameproofing the most according to claim 2, it is characterised in that: in step (2), described
Solvent 2 is oxolane, dichloromethane or chloroform；Described acid binding agent is triethylamine.
The preparation method of a kind of DOPO based flameproofing the most according to claim 2, it is characterised in that: in step (2), described
Phosphoric acid dichloro is 1:(1～4 with the mol ratio of acid binding agent)；Described phosphinylidyne dichloro and acrylate hydroxyl ethyl ester compound mole
Ratio is 1:(1～2)；Described presoma I and acrylate hydroxyl ethyl ester compound equimolar ratio.
The preparation method of a kind of DOPO based flameproofing the most according to claim 2, it is characterised in that: in step (2), institute
The temperature stating ice bath is-10～5 DEG C；Described room temperature is 25 DEG C；The temperature that described rotation is steamed is 40～60 DEG C.
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