CN108484879A - A kind of phosphor-containing flame-proof type epoxy prepolymer and preparation method thereof - Google Patents
A kind of phosphor-containing flame-proof type epoxy prepolymer and preparation method thereof Download PDFInfo
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- CN108484879A CN108484879A CN201810374328.8A CN201810374328A CN108484879A CN 108484879 A CN108484879 A CN 108484879A CN 201810374328 A CN201810374328 A CN 201810374328A CN 108484879 A CN108484879 A CN 108484879A
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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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
A kind of phosphor-containing flame-proof type epoxy prepolymer of present invention offer and preparation method thereof, the phosphor-containing flame-proof type ring oxygen prepolymer structure is novel, it can increase its flame retardant property after polyamide material is added, reduce the additive amount of other fire retardants, while the mechanical strength of polyamide material can also be improved.In addition, the epoxy prepolymer of flame retardant type provided by the invention can prepare fire-retardant epoxy resin as the monomer of fire-retardant epoxy resin, the introducing of fire retardant and halogen is avoided.The preparation method, synthetic method is simple, at low cost.
Description
Technical field
The invention belongs to polymeric additive field, it is related to a kind of phosphor-containing flame-proof type epoxy prepolymer and preparation method thereof.
Background technology
Polyamide (PA) master link contains polar amide groups (- CO-NH -), including polycaprolactam (PA6), polyamides
The kinds such as amine 66 (PA66), polyamide 1010 (PA1010) have excellent mechanical property, are provided simultaneously with wear-resisting, oil resistant, Zi Run
The features such as sliding, the fields such as mechanical equipment, electric, automobile making, fibrous woven are widely used in, are the maximum engineering plastics of dosage
One of material.
But polyamide flame retardant property is poor, and melting drippage is easy in burning, must be carried out in practical applications to it
It is flame-retardant modified to can be only achieved safety requirements.Currently used polyamide fire retardant is mostly halogen containing flame-retardant, and does not meet environmental protection
It is required that.The use of fire retardant can usually reduce mechanical property, the processing performance etc. of polyamide.The exploitation of Non-halogen Flame Retardant Technology is poly-
The important topic of amide application field.
Polyamide is easy to happen degradation during melt-processed, leads to molecular chain rupture, molecular weight and molecular weight, finally makes production
The performance of product declines.The polyamide of reclaiming, because it passes through one or many melt-processeds, molecular degradation is more serious.
The polyamide of regeneration or recycling can not be applied in the higher occasion of performance requirement, in some instances it may even be possible to by as offal treatment, this
It is inconsistent with the theme of current green and low carbon development.Therefore, the molecular weight of polyamide is improved by effective method and glued
Degree, processing technology and recycling for polyamide have great meaning.
In addition, common epoxy resin such as bisphenol A type epoxy resin etc. is all inflammable thing, it usually needs addition fire retardant,
Flame retardant type curing agent is added or halogen-containing monomer prepares fire-retardant epoxy resin, such as brominated epoxy resin etc., these can
The mechanical strength of resin itself can be influenced, or make naval stores that environmental requirement be not achieved.So developing the ring of flame retardant type
Oxygen prepolymer monomer is of great significance to fire-retardant epoxy resin.
Polyamide flame retardant property is poor, it is necessary to be carried out to it flame-retardant modified, halogen-free flame retardants flame retarding efficiency is relatively low, usually needs
The requirement for largely reaching sufficient practical application is added, mechanical strength and processing performance of polyamide etc. can be reduced in this way.Fire retardant
Thermal decomposition, flavescence, precipitation etc. be also the larger problem faced at present.Lance between the flame retardant property and mechanical property of polyamide
Shield solution not very ideal so far.
It is the effective ways for enhancing its mechanical strength to improve polyamide relative molecular weight.The method for improving relative molecular weight has
Extend melt polycondensation time and solid phase, preceding kind of method in polycondensation reaction later stage material large viscosity, stirring and by-product
Diffusion is difficult, and reaction speed is slow, and the side reactions aggravation such as degradation, properties of product decline；The latter's solid-phase polymerization speed is slow, big to advise
Mould production needs dedicated equipment, thus limits its application.Chemical chain extension method be a kind of simple and effective improve polyamide
The method of molecular weight and viscosity issues biochemical reaction in molten polyamide state by the way that chain extender is added, improves strand.It
Have the characteristics that reaction speed is fast, processing is flexible, at low cost, the equipment continuous production such as screw extruder can be passed through.
Currently, chain extender in the market is of less types, have a single function, chain extension effect is also undesirable, and has combustion-supporting work
With increasing fire-retardant difficulty.The styrene-t glycidol ester oligomer ADR series of BASF, because containing more
A epoxy-functional easy tos produce branched cross-linked structure, melt viscosity is made constantly to increase with the extension of melt-processed time,
It is difficult to control.
CN103897385A " a kind of fire-retardant chain extension nylon 6 composition and preparation method thereof " discloses a kind of fire-retardant and chain extension
The nylon 6 composition being combined, chain extender used are phosphorous epoxide P-EP, contain-SO in molecule2Group, and lead to
Cross phospho hetero phenanthrene structure on schiff base structure reaction forming.Schiff base reaction mechanism is the nitrogen-atoms attack carbonyl with lone pair electrons pair
The carbon atom that positive charge is carried on base, completes nucleophilic addition, then be dehydrated and to form schiff base structure.-SO2The suction electricity of group
Sub- ability is stronger so that the cloud density of amino declines, and reactivity becomes smaller.In addition, the steric hindrance effect of phospho hetero phenanthrene building stone
It answers larger, the activity of phenolic hydroxyl group and epoxy group necleophilic reaction below can be influenced.
Invention content
For the technical problems in the prior art, a kind of phosphor-containing flame-proof type epoxy prepolymer of present invention offer and its system
Preparation Method, the phosphor-containing flame-proof type ring oxygen prepolymer structure is novel, can increase its flame retardant property after polyamide material is added, and reduces
The additive amount of other fire retardants, while the mechanical strength of polyamide material can also be improved.The preparation method, synthetic method letter
It is single, it is at low cost.
In order to achieve the above objectives, the present invention uses following technical scheme：
It is an object of the present invention to provide a kind of phosphor-containing flame-proof type epoxy prepolymers, and the structure of the epoxy prepolymer is such as
Shown in Formulas I：
Wherein, X1 is
Y1 is substituted or unsubstituted arlydene or substituted or unsubstituted inferior heteroaryl, m and p be separately more than
Integer equal to 1；
A1 be substituted or unsubstituted alkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl,
Substituted or unsubstituted Asia biaryl, substituted or unsubstituted sub- connection heteroaryl, substituted or unsubstituted sub- oxygen biaryl, substitution
Or unsubstituted sub- oxygen connection heteroaryl, substituted or unsubstituted sub- (imino group biaryl), substituted or unsubstituted sub- (imino group
Join heteroaryl), in substituted or unsubstituted sub- (alkylidene biaryl) or substituted or unsubstituted sub- (alkylidene connection heteroaryl)
Any one.
Wherein, m can be 1,2,3,5,10,20 or 50 etc., and p can be 1,2,3,4,5,6,7,8,9 or 10 etc., but not
It is only limitted to cited numerical value, other unrequited numerical value are equally applicable in above-mentioned each numberical range.P should be less than Y1Middle carbon atom
Sum.
As currently preferred technical solution, the N atoms in the X1 are connected with Y1 or A1 groups.
As currently preferred technical solution, the substituent group of the A1 include substituted or unsubstituted alkyl, substitution or
Unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted alcoxyl
Base, substituted or unsubstituted aryloxy group, substituted or unsubstituted heteroaryloxy, takes substituted or unsubstituted cycloalkyloxy
Generation or unsubstituted alkylamino, substituted or unsubstituted naphthene amino, substituted or unsubstituted fragrant amino, substitution or do not take
It is the heteroaryl amino in generation, substituted or unsubstituted alkyl thiol, substituted or unsubstituted aryl thiol, substituted or unsubstituted miscellaneous
Aromatic thiohydroxy, substituted or unsubstituted carboxylate, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group or
In substituted or unsubstituted phosphonate group any one or at least two combination.
Phosphor-containing flame-proof type epoxy prepolymer provided by the invention, it is characterized in that respectively there are one epoxy groups at molecule both ends, it can
It is reacted with the amino and carboxyl with the polyamide end of the chain, molecular weight is improved, to increase the mechanical strength of polyamide, while handle
Phospho hetero phenanthrene structure is introduced into strand, plays certain fire retardation, it is possible to reduce the additive amount of fire retardant can also improve
The mechanical strength of polyamide.
As currently preferred technical solution, the alkylidene is preferably the linear chain or branched chain alkylidene of C1~C12；
Preferably, the substituted or unsubstituted inferior heteroaryl includes C5~C13 substituted or unsubstituted miscellaneous
Aryl；
Preferably, the substituted or unsubstituted sub- biaryl includes the substituted or unsubstituted sub- biaryls of C12~C18；
Preferably, the substituted or unsubstituted sub- substituted or unsubstituted sub- connection heteroaryls of connection heteroaryl C10~C18；
Preferably, the substituted or unsubstituted sub- oxygen biaryl includes the substituted or unsubstituted sub- oxygen biaryls of C12~C18
Base；
Preferably, the substituted or unsubstituted sub- oxygen connection heteroaryl includes the substituted or unsubstituted sub- oxygen connection of C10~C18
Heteroaryl；
Preferably, substituted or unsubstituted sub- (the imino group biaryl) includes the substituted or unsubstituted Asias C12~C18
(imino group biaryl)；
Preferably, substituted or unsubstituted sub- (the imino group connection heteroaryl) includes C10~C18 substituted or unsubstituted
Sub- (imino group connection heteroaryl)；
Preferably, substituted or unsubstituted sub- (the alkylidene biaryl) includes the substituted or unsubstituted Asias C13~C20
(alkylidene biaryl)；
Preferably, substituted or unsubstituted sub- (the alkylidene connection heteroaryl) includes C11~C20 substituted or unsubstituted
Sub- (alkylidene connection heteroaryl).
As currently preferred technical solution, the A1 includes sub- (4- oxygen xenyl), sub- (3- melamines
Base) or sub- (4- xenyls) in any one.
Preferably, the Y1 includes Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-naphthylene, the Asias 3,5- pyrazoles, 2,5- furylidenes, the Asias 2,5-
Any one in thienyl, 2,4- sub-pyridyl groups, the Asias 2,4- imidazole radicals or 2,4- Ya oxazolyls.
As currently preferred technical solution, the epoxy prepolymer includes：
In any one.
In the present invention, substituted or unsubstituted alkyl be preferably C1~C12 (such as C2, C3, C4, C5, C6, C7,
C8, C9, C10 or C11) alkyl.
Substituted or unsubstituted naphthenic base is preferably C3~C12 (such as C4, C5, C6, C7, C8, C9, C10 or C11)
Naphthenic base.
Substituted or unsubstituted aryl is preferably the aryl of C6~C13 (such as C7, C8, C9, C10, C11 or C12).
Substituted or unsubstituted heteroaryl is preferably C5~C13 (such as C6, C7, C8, C9, C10, C11 or C12) substitutions
Or unsubstituted heteroaryl.
The substituted or unsubstituted alkoxy be preferably C1~C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) substituted or unsubstituted alkoxy.
Substituted or unsubstituted cycloalkyloxy is preferably C3~C12 (such as C4, C5, C6, C7, C8, C9, C10 or C11)
Substituted or unsubstituted cycloalkyloxy.
Substituted or unsubstituted aryloxy group be preferably C6~C13 (such as C7, C8, C9, C10, C11 or C12) substitution or
Unsubstituted aryloxy group.
Substituted or unsubstituted heteroaryloxy is preferably that C5~C13 (such as C6, C7, C8, C9, C10, C11 or C12) takes
Generation or unsubstituted heteroaryl.
The substituted or unsubstituted alkylamino be preferably C1~C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) substituted or unsubstituted alkylamino.
Substituted or unsubstituted naphthene amino is preferably C3~C12 (such as C4, C5, C6, C7, C8, C9, C10 or C11)
Substituted or unsubstituted naphthene amino.
Substituted or unsubstituted fragrant amino be preferably C6~C13 (such as C7, C8, C9, C10, C11 or C12) substitution or
Unsubstituted fragrant amino.
Substituted or unsubstituted heteroaryl amino is preferably C5~C13 (such as C8, C9, C10, C11 or C12) substitutions or does not take
The heteroarylalkylamino in generation.
Substituted or unsubstituted alkyl thiol C1~C12 (such as C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) takes
Generation or unsubstituted alkyl thiol.
Substituted or unsubstituted aryl thiol be preferably C6~C13 (such as C7, C8, C9, C10, C11 or C12) substitution or
Unsubstituted aryl thiol.
Substituted or unsubstituted heteroaryl sulfydryl is preferably C5~C13 (such as C8, C9, C10, C11 or C12) substitutions or does not take
The heteroarylalkylamino in generation.
Substituted or unsubstituted carboxylate is preferably what C2~C8 (such as C2, C3, C4, C5, C6, C7 or C8) replaced
Or unsubstituted carboxylate.
Substituted or unsubstituted carbonate group is preferably what C2~C8 (such as C2, C3, C4, C5, C6, C7 or C8) replaced
Or unsubstituted carbonate group.
Substituted or unsubstituted sulfonate group is preferably what C1~C8 (such as C2, C3, C4, C5, C6, C7 or C8) replaced
Or unsubstituted sulfonate group.
It is substituted or unsubstituted it is phosphate-based preferably C1~C6 (such as C2, C3, C4, C5 or C6) substitution or do not take
Generation it is phosphate-based.
The second purpose of the present invention is to provide a kind of preparation methods of above-mentioned epoxy prepolymer, and the method includes following steps
Suddenly：
(1) it is mixed by the compound containing A1 groups, with the compound containing Y1 groups and solvent, 9 is added after reaction,
The reaction was continued for the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 10- dihydro-9-oxies, and separation of solid and liquid obtains intermediate；
(2) intermediate that step (1) obtains is mixed with catalyst, solvent and epoxychloropropane, alkali is added after reaction
The reaction was continued for aqueous solution, and separation of solid and liquid obtains the phosphor-containing flame-proof type epoxy prepolymer.
As currently preferred technical solution, the compound containing A1 groups described in step (1) is that A1 groups connect two
A amino is formed by compound or A1 groups connect two aldehyde radicals and are formed by compound.
Preferably, the compound containing Y1 groups described in step (1) be containing at least one hydroxyl and aromatic rings at least
It connects there are one the aromatic compound of aldehyde radical, contain the fragrance for being at least connected with an amino at least one hydroxyl and aromatic rings
Compound containing the heteroaryl compound for being at least connected with aldehyde radical at least one hydroxyl and heteroaryl or contains at least one hydroxyl
The heteroaryl compound of an amino is at least connected on base and heteroaryl.
In preparation method of the present invention, in order to obtain schiff base structure, A1 groups should be used to connect two amino institutes
The compound of formation with containing the aromatic compound for being at least connected with aldehyde radical at least one hydroxyl and aromatic rings or contain
The heteroaryl compound reaction of an aldehyde radical is at least connected at least one hydroxyl and heteroaryl.Or connect two using A1 groups
Aldehyde radical is formed by the aromatic compound that amino is at least connected on compound and at least one hydroxyl and aromatic rings or extremely
The heteroaryl compound reaction of an amino is at least connected on a few hydroxyl and heteroaryl.
Preferably, the molar ratio of the compound containing A1 groups and the compound containing Y1 groups is 1:(2~
3), such as 1:2、1:2.1、1:2.2、1:2.3、1:2.4、1:2.5、1:2.6、1:2.7、1:2.8、1:2.9 or 1:3 etc., but not
It is only limitted to cited numerical value, other unrequited numerical value are equally applicable in the numberical range.
Preferably, step (1) described solvent includes methanol, ethyl alcohol, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, N, N- dimethyl
In formamide, dichloromethane or chloroform any one or at least two combination, the combination is typical but non-limiting
Example has：The combination of methanol and ethyl alcohol, the combination of ethyl alcohol and tetrahydrofuran, the combination of tetrahydrofuran and 1,4- dioxane, 1,
The combination of 4- dioxane and N,N-dimethylformamide, dichloromethane and the combination or methanol of chloroform, ethyl alcohol and tetrahydrochysene
The combination etc. of furans.
Preferably, step (1) is described is added the temperature reacted before 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
Degree is 40~120 DEG C, such as 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C or 120 DEG C, but is simultaneously not only limited
It is equally applicable in other unrequited numerical value in cited numerical value, the numberical range.
Preferably, step (1) it is described be added 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide before react when
Between be 2~5h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, it is not limited to cited numerical value, the numberical range
Other interior unrequited numerical value are equally applicable.
Preferably, step (1) is described is added the temperature reacted after 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
Degree is 20~50 DEG C, such as 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C or 50 DEG C, it is not limited to cited number
Value, other interior unrequited numerical value of the numberical range are equally applicable.
Preferably, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide of addition with contain A1 groups
The ratio between amount of substance of compound is (1~1.2):1, such as 1:1、1.02:1、1.05:1、1.08:1、1.1:1、1.12:1、
1.25:1、1.18:1 or 1.2 etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are same
Sample is applicable in.
Preferably, step (1) it is described be added 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide after react when
Between be 8~14h, such as 8h, 9h, 10h, 11h, 12h, 13h or 14h, it is not limited to cited numerical value, the numberical range
Other interior unrequited numerical value are equally applicable.
Preferably, the method for step (1) described separation of solid and liquid is any one in sedimentation, filtering or centrifugation or at least two
The combination of kind, the combination is typical but non-limiting examples have：Combination, the sedimentation of combination, filtering and the centrifugation of sedimentation and filtering
The combination etc. of combination or sedimentation, filtering and centrifugation with centrifugation.
As currently preferred technical solution, step (2) described catalyst is alkali.
Preferably, the alkali be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or triethylamine in any one or
At least two combination, the combination is typical but non-limiting examples have：The combination of sodium hydroxide and potassium hydroxide, sodium hydroxide
The combination etc. of combination or sodium carbonate and calcium carbonate with sodium carbonate.
Preferably, the ratio between step (2) intermediate and the amount of substance of the catalyst are 1:1.
Preferably, step (2) described solvent includes methanol, ethyl alcohol, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, N, N- dimethyl
In formamide, dichloromethane or chloroform any one or at least two combination, the combination is typical but non-limiting
Example has：The combination of methanol and ethyl alcohol, the combination of ethyl alcohol and tetrahydrofuran, the combination of tetrahydrofuran and 1,4- dioxane, 1,
The combination of 4- dioxane and N,N-dimethylformamide, dichloromethane and the combination or methanol of chloroform, ethyl alcohol and tetrahydrochysene
The combination etc. of furans.
Preferably, the ratio between amount of substance of step (2) intermediate and epoxychloropropane is 1:(2~15), such as 1:2、
1:3、1:4、1:5、1:6、1:7、1:8、1:9、1:10、1:11、1:12、1:13、1:14 or 1:15 etc., it is not limited to listed
The numerical value of act, other interior unrequited numerical value of the numberical range are equally applicable.
The epichlorohydrin reaction of the amount of different material is added in step (2) of the present invention, can obtain the ring of different polymer
Oxygen prepolymer.The amount of epoxychloropropane is fewer, and the degree of polymerization is higher.When the amount of epoxychloropropane is more than or equal to 8 times of substances
When amount, largely autohemagglutination does not occur for obtained epoxy prepolymer, and state is solid powder, suitable for polyamide
Chain extender.When the amount of epoxychloropropane is about the amount of 3 times of substances, obtained epoxy prepolymer has higher polymerization
Object, state are viscous oil-like liquid, are suitable for fire-retardant epoxy resin.
Preferably, the temperature of step (2) described reaction be 40~120 DEG C, such as 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90
DEG C, 100 DEG C, 110 DEG C or 120 DEG C etc., it is not limited to cited numerical value, other unrequited numerical value in the numberical range
It is equally applicable.
Preferably, step (2) it is described be added alkali aqueous solution before reaction time be 2~5h, as 2h, 2.5h, 3h,
3.5h, 4h, 4.5h or 5h etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are same
It is applicable in.
Preferably, step (2) it is described be added alkali aqueous solution after reaction time be 4~8h, as 4h, 4.5h, 5h,
5.5h, 6h, 6.5h, 7h, 7.5h or 8h etc., it is not limited to cited numerical value, other are unrequited in the numberical range
Numerical value is equally applicable.
Preferably, the aqueous solution of step (2) described alkali is sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution.
Preferably, in the aqueous solution of step (2) described alkali alkali mass fraction be 30%~50%, such as 30%, 35%,
40%, 45% or 50% etc., it is not limited to cited numerical value, other interior unrequited numerical value of the numberical range are equally suitable
With.
Preferably, the ratio between the addition with the amount of substance of the intermediate of alkali are in the aqueous solution of step (2) described alkali
(3~6):1, such as 3:1、3.5:1、4:1、4.5:1、5.5:1 or 6:1 etc., it is not limited to cited numerical value, the numerical value model
Other unrequited numerical value are equally applicable in enclosing.
Preferably, the method for step (2) described separation of solid and liquid is any one in sedimentation, filtering or centrifugation or at least two
The combination of kind, the combination is typical but non-limiting examples have：Combination, the sedimentation of combination, filtering and the centrifugation of sedimentation and filtering
The combination etc. of combination or sedimentation, filtering and centrifugation with centrifugation.
As currently preferred technical solution, the described method comprises the following steps：
(1) according to molar ratio 1:(2~3) are by the compound containing A1 groups and compound and solvent containing Y1 groups
It mixes, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added after reacting 2~5 hour hour at 40~120 DEG C,
The reaction was continued at 20~50 DEG C 8~14 hour hour, is separated by solid-liquid separation, obtains intermediate；
(2) intermediate and catalyst for obtaining equimolar step (1), with the amount of solvent and the intermediate materials
2~15 times of epoxychloropropane mixes, and the reaction was continued 4~8 hours for the aqueous solution of addition alkali after being reacted .. hours at 40~120 DEG C
Hour, separation of solid and liquid obtains the phosphor-containing flame-proof type epoxy prepolymer.
Compared with prior art, the present invention at least has the advantages that：
The phosphor-containing flame-proof type ring oxygen prepolymer structure of the present invention is novel, and raw material is cheap, and synthesis is easy, and cost is relatively low.It can be with
It is reacted by the amino and carboxyl with the polyamide molecule end of the chain, molecular weight is improved, to increase the machinery of polyamide material
Intensity.On the other hand, polyamide material can be made to have certain fire retardation, reduces the additive amount of fire retardant, can also carried
The mechanical strength of super polyamide material.In addition, the epoxy prepolymer of flame retardant type provided by the invention can be used as flame retardant type epoxy
The monomer of resin prepares fire-retardant epoxy resin, avoids the introducing of fire retardant and halogen.
Description of the drawings
Fig. 1 is the intermediate that embodiment 1 is prepared1H NMR figures；
Fig. 2 is the phosphor-containing flame-proof type epoxy prepolymer that embodiment 1 is prepared1H NMR figures；
Fig. 3 is the infrared spectrogram for the phosphor-containing flame-proof type epoxy prepolymer that embodiment 1 is prepared.
The present invention is described in more detail below.But following examples is only the simple example of the present invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific implementation mode
For the present invention is better described, it is easy to understand technical scheme of the present invention, of the invention is typical but non-limiting
Embodiment is as follows：
Embodiment 1
The present embodiment provides a kind of phosphor-containing flame-proof type epoxy prepolymers, and structure is as shown in Formula II：
The preparation method of the phosphor-containing flame-proof type epoxy prepolymer is：
Step (1)：22.623g (0.10mol) is added in the 1L three neck round bottom flask with condenser pipe to 4- (4- formoxyls
Phenoxy group) benzaldehyde, 21.86g (0.20mol) 4-aminophenol and 500mL ethyl alcohol is warming up to 50 DEG C under the protection of nitrogen,
It is stirred to react 5 hours.It is cooled to room temperature, 43.28g (0.20mol) DOPO is added, reacts 12 under nitrogen atmosphere and magnetic agitation
Hour, it after reaction, filters and removes filtrate, filter residue is washed 3 times with ethyl alcohol, intermediate is obtained after dry.Reaction equation is such as
Shown in formula III.
1H NMR(300MHz,DMSO)δppm:8.48(2H,s,-OH),8.19(2H,m,DOPO),8.17(2H,m,
DOPO),8.06(2H,m,DOPO),7.96(2H,s,-NH-),7.79(2H,m,DOPO),7.45(2H,m,DOPO),7.35
(4H,d,phenyl),7.32(2H,m,DOPO),7.10(2H,m,DOPO),6.84(4H,d,phenyl),6.52(4H,d,
phenyl),6.40(4H,m,phenyl),5.00(2H,m,Methine).
Step (2)：It is added on 13.89g (0.034mol) and walks in the 500mL three-necked flasks with condenser pipe and dropping funel
46.3g (0.5mol) epoxy is added after stirring and dissolving for rapid intermediate, 1.9g (0.034mol) potassium hydroxide and 200mL ethyl alcohol
Chloropropane is warming up to 60 DEG C and reacts 3 hours under nitrogen protection.It is 40% that 19.0g mass fractions are added dropwise in 1 hour again
Potassium hydroxide aqueous solution (0.136mol potassium hydroxide) is warming up to 75 DEG C and reacts 5 hours after being added dropwise.It is taken out after being cooled to room temperature
Leaching filter residue is washed with distilled water filter residue to filter liquor and shows neutrality, is dried in vacuo at 80 DEG C and obtains target product.Reaction equation
As shown in formula IV.FTIR(cm-1):3500-3300 (- OH str.), 1499 (- CH=N str.), 1243 (- C-O-C-,
str.),828(epoxy ring str.)。
Embodiment 2
The present embodiment provides the one epoxy type epoxy prepolymer containing schiff base structure, structure are shown as a formula V：
Synthetic method is as follows：
Step (1)：18.72g (0.10mol) 2,4- diamino -6- is added in the 1L three neck round bottom flask with condenser pipe
Phenyl -1,3,5-triazines, 24.40g (0.25mol) parahydroxyben-zaldehydes and 500mL ethyl alcohol are warming up under the protection of nitrogen
It 50 DEG C, is stirred to react 5 hours.It is cooled to room temperature, 43.28g (0.20mol) DOPO is added, under nitrogen atmosphere and magnetic agitation
Reaction 12 hours filters after reaction and removes filtrate, filter residue is washed 3 times with ethyl alcohol, and intermediate is obtained after dry.Reaction side
Formula is as shown in Formula IV.
1H NMR(300MHz,DMSO)δppm:9.16(2H,s,-OH),8.36(2H,d,phenyl),8.00(4H,d,
DOPO),7.75(4H,d,DOPO),7.50-7.38(15H,m,phenyl+DOPO),7.11(4H,d,phenyl),6.80(s,
2H,-NH-),6.75(d,4H),3.91(2H,s)。
Step (2)：It is added on 28.14g (0.034mol) and walks in the 500mL three-necked flasks with condenser pipe and dropping funel
46.3g (0.5mol) epoxy chlorine is added after stirring and dissolving for rapid intermediate, 1.9g (0.034mol) potassium hydroxide and 200m L ethyl alcohol
Propane is warming up to 60 DEG C and reacts 3 hours under nitrogen protection.The hydrogen that 19.0g mass fractions are 40% is added dropwise in 1 hour again
Aqueous solutions of potassium (0.136mol potassium hydroxide) is aoxidized, 75 DEG C are warming up to after being added dropwise and is reacted 5 hours.It is filtered after being cooled to room temperature
Filter residue is taken, filter residue to filter liquor is washed with distilled water and shows neutrality, be dried in vacuo at 80 DEG C and obtain product DTS.Reaction equation is such as
Shown in formula IV.
Embodiment 3
The present embodiment provides the one epoxy type epoxy prepolymer containing schiff base structure, structure is as shown in Formula VIII：
Synthetic method is as follows：
Step (1)：In the 1L three neck round bottom flask with condenser pipe be added 18.42g (0.10mol) benzidine,
30.78g (0.25mol) 6- pyridone -3- formaldehyde and 500mL ethyl alcohol are warming up to 50 DEG C, stirring is anti-under the protection of nitrogen
It answers 5 hours.It is cooled to room temperature, 43.28g (0.20mol) DOPO is added, is reacted 12 hours under nitrogen atmosphere and magnetic agitation,
After reaction, it filters and removes filtrate, filter residue is washed 3 times with ethyl alcohol, intermediate is obtained after dry.Reaction equation such as Formula IX institute
Show.
1H NMR(300MHz,DMSO)δppm:10.97(2H,s),8.10(2H,s,),7.70-7.45(4H,m),7.50-
7.25(22H,m),6.75(2H,s),3.91(2H,s)。
Step (2)：It is added on 13.41g (0.034mol) and walks in the 500mL three-necked flasks with condenser pipe and dropping funel
46.3g (0.5mol) epoxy chlorine is added after stirring and dissolving for rapid intermediate, 1.9g (0.034mol) potassium hydroxide and 200m L ethyl alcohol
Propane is warming up to 60 DEG C and reacts 3 hours under nitrogen protection.The hydrogen that 19.0g mass fractions are 40% is added dropwise in 1 hour again
Aqueous solutions of potassium (0.136mol potassium hydroxide) is aoxidized, 75 DEG C are warming up to after being added dropwise and is reacted 5 hours.It is filtered after being cooled to room temperature
Filter residue is taken, filter residue to filter liquor is washed with distilled water and shows neutrality, be dried in vacuo at 80 DEG C and obtain product DBPS.Reaction equation is such as
Shown in Formula X.
1H NMR(300MHz,DMSO)δppm:8.97 (2H, s ,-CH=N-), 8.10 (4H, d, phenyl), 7.98 (4H,
d,phenyl),7.55(2H,m),7.35(2H,m),6.66(4H,d,phenyl),4.35(4H,d,-O-CH2-),4.00(2H,
d,epoxy ring),3.86(4H,d,epoxy ring)。
Embodiment 4
The epoxy prepolymer that embodiment 1 is prepared the present embodiment is in polyamide 6 halogen-free flameproof formula.A combination thereof
Object includes following components (calculating as mass fraction)：Polyamide 6,85 parts；Diethyl hypo-aluminum orthophosphate, 13 parts；Epoxy prepolymer, 2
Part.LOI values are that 34%, UL-94 grades are V0@1.6mm, no molten drop phenomenon.Tensile strength is 52.7MPa, and bending strength is
74.1MPa, notch impact strength 77.1Jm-1, melt flow rate (MFR) is 16.4g (10min)-1。
Correction data without above-mentioned epoxy prepolymer component：Polyamide 6,87 parts；Diethyl hypo-aluminum orthophosphate, 13 parts.LOI values
It is V2@1.6mm for 29.3%, UL-94 grades, there is molten drop phenomenon.Tensile strength is 45.5MPa, bending strength 60.3MPa,
Notch impact strength is 70.7Jm-1, melt flow rate (MFR) is 24.1g (10min)-1。
Embodiment 5
The epoxy prepolymer that embodiment 1 is prepared the present embodiment is used for 66 halogen-free flameproof formula of fiber glass reinforced polyamide
In.Its composition includes following components (calculating as mass fraction)：Polyamide 66,58 parts；Glass, 25 parts；Melamine poly
Phosphate, 15 parts；Epoxy prepolymer, 2 parts.LOI values are that 32.4%, UL-94 grades are V0@1.6mm, no molten drop phenomenon.It stretches
Intensity is 114.3MPa, bending strength 152.4MPa, notch impact strength 11.5Jm-1。
Correction data without above-mentioned epoxy prepolymer component：Polyamide 66,60 parts；Glass, 25 parts；Melamine poly phosphorus
Hydrochlorate, 15 parts.LOI values are that 20.4%, UL-94 grades are V2@1.6mm, there is molten drop phenomenon.Tensile strength is 100.6MPa, curved
Qu Qiangdu is 138.3MPa, notch impact strength 10.2Jm-1。
Embodiment 6
The epoxy prepolymer that embodiment 2 is prepared the present embodiment is in polyamide 6 halogen-free flameproof formula.A combination thereof
Object includes following components (calculating as mass fraction)：Polyamide 6,85 parts；Diethyl hypo-aluminum orthophosphate, 13 parts；Epoxy prepolymer, 2
Part.LOI values are that 37.4%, UL-94 grades are V0@1.6mm, no molten drop phenomenon.Tensile strength is 53.4MPa, and bending strength is
60.2MPa, notch impact strength 87.4Jm-1, melt flow rate (MFR) is 18.4g (10min)-1。
Correction data：Polyamide 6,87 parts；Diethyl hypo-aluminum orthophosphate, 13 parts, ADR, 0.5 part.LOI values are 28.5%, UL-
94 grades are V2@1.6mm, there is molten drop phenomenon.Tensile strength is 50.2MPa, bending strength 64.4MPa, notch impact strength
For 77.3Jm-1, melt flow rate (MFR) is 19.4g (10min)-1。
Embodiment 7
The epoxy prepolymer that embodiment 1 is prepared the present embodiment is used for 66 halogen-free flameproof formula of fiber glass reinforced polyamide
In.Its composition includes following components (calculating as mass fraction)：Polyamide 66,58 parts；Glass, 25 parts；Melamine poly
Phosphate, 15 parts；Epoxy prepolymer, 2 parts.LOI values are that 29.3%, UL-94 grades are V0@1.6mm, no molten drop phenomenon.It stretches
Intensity is 118.2MPa, bending strength 137.2MPa, notch impact strength 12.5Jm-1。
Correction data without above-mentioned epoxy prepolymer component：Polyamide 66,60 parts；Glass, 25 parts；Melamine poly phosphorus
Hydrochlorate, 15 parts.LOI values are that 20.4%, UL-94 grades are V2@1.6mm, there is molten drop phenomenon.Tensile strength is 100.6MPa, curved
Qu Qiangdu is 138.3MPa, notch impact strength 10.2.Jm-1。
Embodiment 8
The epoxy prepolymer that embodiment 3 is prepared is used for polybutylene terephthalate (PBT) (PBT) halogen-free flameproof formula
In.Its composition includes following components (calculating as mass fraction)：PBT, 86 parts；Diethyl hypo-aluminum orthophosphate, 12 parts；Epoxy pre-polymerization
Object, 3 parts.LOI values are that 36.9%, UL-94 grades are V0@1.6mm, no molten drop phenomenon.Tensile strength is 52.5MPa, and bending is strong
Degree is 85.7MPa, notch impact strength 40.8Jm-1, melt flow rate (MFR) is 18.4g (10min)-1。
Correction data without above-mentioned epoxy prepolymer component：PBT, 87 parts；Diethyl hypo-aluminum orthophosphate, 13 parts.LOI values are
34.3%, UL-94 grade are V1@1.6mm, there is molten drop phenomenon.Tensile strength is 47.6MPa, bending strength 80.3MPa, is lacked
Mouth impact strength is 39.7Jm-1, melt flow rate (MFR) is 20.4g (10min)-1。
Embodiment 9
The epoxy prepolymer that embodiment 3 is prepared is in polylactic acid (PLA) formula.Its composition includes following components
(calculating as mass fraction)：PLA, 85 parts；Diethyl hypo-aluminum orthophosphate, 13 parts；Epoxy prepolymer, 2 parts.LOI values are 34.8%,
UL-94 grades are V0@1.6mm, no molten drop phenomenon.Tensile strength is 67.1MPa, bending strength 73.2MPa, and notch shock is strong
Degree is 2.12Jm-1, melt flow rate (MFR) is 19.6g (10min)-1。
Correction data without above-mentioned epoxy prepolymer component：PLA, 87 parts；Diethyl hypo-aluminum orthophosphate, 13 parts.LOI values are
24.2%, UL-94 grade are V1@1.6mm, there is molten drop phenomenon.Tensile strength is 60.1MPa, bending strength 77.3MPa, is lacked
Mouth impact strength is 2.6Jm-1, melt flow rate (MFR) is 23.4g (10min)-1。
Applicant states that the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
It is not limited to above-mentioned detailed construction feature, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implement.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of component selected by the present invention
And the increase of accessory, the selection etc. of concrete mode, it all falls within protection scope of the present invention and the open scope.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of phosphor-containing flame-proof type epoxy prepolymer, which is characterized in that the structure of the epoxy prepolymer is shown in formula I：
Wherein, X1 is
Y1 is substituted or unsubstituted arlydene or substituted or unsubstituted inferior heteroaryl, m and p be separately more than or equal to
1 integer；
A1 is substituted or unsubstituted alkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substitution
Or unsubstituted sub- biaryl, substituted or unsubstituted sub- connection heteroaryl, substituted or unsubstituted sub- oxygen biaryl, substitution or not
Substituted sub- oxygen connection heteroaryl, substituted or unsubstituted sub- (imino group biaryl), substituted or unsubstituted sub- (imino group connection is miscellaneous
Aryl), appointing in substituted or unsubstituted sub- (alkylidene biaryl) or substituted or unsubstituted sub- (alkylidene connection heteroaryl)
Meaning is a kind of.
2. epoxy prepolymer according to claim 1, which is characterized in that the N atoms in the X1 and Y1 or A1 group phases
Even.
3. epoxy prepolymer according to claim 1 or 2, which is characterized in that the substituent group of the A1 is including substitution or not
Substituted alkyl, substituted or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl,
Substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryloxy group, substitution or not
Substituted heteroaryloxy, substituted or unsubstituted alkylamino, substituted or unsubstituted naphthene amino, substituted or unsubstituted virtue
Amino, substituted or unsubstituted heteroaryl amino, substituted or unsubstituted alkyl thiol, substituted or unsubstituted aryl thiol,
Substituted or unsubstituted heteroaryl sulfydryl, substituted or unsubstituted carboxylate, substituted or unsubstituted carbonate group, substitution or
In unsubstituted sulfonate group or substituted or unsubstituted phosphonate group any one or at least two combination.
4. according to claim 1-3 any one of them epoxy prepolymers, which is characterized in that the alkylidene be preferably C1~
The linear chain or branched chain alkylidene of C12；
Preferably, the substituted or unsubstituted inferior heteroaryl includes the substituted or unsubstituted heteroaryls of C5~C13；
Preferably, the substituted or unsubstituted sub- biaryl includes the substituted or unsubstituted sub- biaryls of C12~C18；
Preferably, the substituted or unsubstituted sub- substituted or unsubstituted sub- connection heteroaryls of connection heteroaryl C10~C18；
Preferably, the substituted or unsubstituted sub- oxygen biaryl includes the substituted or unsubstituted sub- oxygen biaryls of C12~C18；
Preferably, the substituted or unsubstituted sub- oxygen connection heteroaryl includes the substituted or unsubstituted sub- oxygen connection heteroaryls of C10~C18
Base；
Preferably, substituted or unsubstituted sub- (the imino group biaryl) includes C12~C18 substituted or unsubstituted sub- (sub-
Amino biaryl)；
Preferably, substituted or unsubstituted sub- (the imino group connection heteroaryl) includes the substituted or unsubstituted Asias C10~C18
(imino group connection heteroaryl)；
Preferably, substituted or unsubstituted sub- (the alkylidene biaryl) includes C13~C20 substituted or unsubstituted sub- (sub-
Alkyl biaryl)；
Preferably, substituted or unsubstituted sub- (the alkylidene connection heteroaryl) includes the substituted or unsubstituted Asias C11~C20
(alkylidene connection heteroaryl).
5. according to claim 1-4 any one of them epoxy prepolymers, which is characterized in that the A1 includes sub- (4- oxygen biphenyl
Base), any one in sub- (3- melamines base) or sub- (4- xenyls).
Preferably, the Y1 includes Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-naphthylene, the Asias 3,5- pyrazoles, 2,5- furylidenes, the Asias 2,5- thiophene
Any one in base, 2,4- sub-pyridyl groups, the Asias 2,4- imidazole radicals or 2,4- Ya oxazolyls.
6. according to epoxy prepolymers of the claim 1-5 described in any one, which is characterized in that the epoxy prepolymer includes：
In any one.
7. a kind of preparation method of any one of claim 1-6 epoxy prepolymers, which is characterized in that the method includes with
Lower step：
(1) it is mixed by the compound containing A1 groups, with the compound containing Y1 groups and solvent, 9,10- is added after reaction
The reaction was continued for the miscellaneous -10- phospho hetero phenanthrenes -10- oxides of dihydro-9-oxy, and separation of solid and liquid obtains intermediate；
(2) intermediate that step (1) obtains is mixed with catalyst, solvent and epoxychloropropane, the water-soluble of alkali is added after reaction
The reaction was continued for liquid, and separation of solid and liquid obtains the phosphor-containing flame-proof type epoxy prepolymer.
8. preparation method according to claim 7, which is characterized in that the compound containing A1 groups is described in step (1)
A1 groups two amino of connection are formed by compound or A1 groups connect two aldehyde radicals and are formed by compound；
Preferably, the compound containing Y1 groups described in step (1) is containing being at least connected at least one hydroxyl and aromatic rings
There are one be at least connected on the aromatic compound of aldehyde radical, at least one hydroxyl and aromatic rings an amino aromatic compound,
Containing the heteroaryl compound for being at least connected with aldehyde radical at least one hydroxyl and heteroaryl or contain at least one hydroxyl and miscellaneous
The heteroaryl compound of an amino is at least connected on virtue；
Preferably, the molar ratio of the compound containing A1 groups and the compound containing Y1 groups is 1:(2~3)；
Preferably, step (1) described solvent includes methanol, ethyl alcohol, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, N, N- dimethyl formyls
In amine, dichloromethane or chloroform any one or at least two combination；
Preferably, step (1) temperature reacted before 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide that is added is
40~120 DEG C；
Preferably, the time reacted before step (1) the addition 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 2
~5 hours；
Preferably, step (1) temperature reacted after 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide that is added is
20~50 DEG C；
Preferably, step (1) be added the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with contain A1 bases
The ratio between amount of substance of compound of group is (1~1.2):1.
Preferably, the time reacted after step (1) the addition 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 8
~14 hours.
Preferably, the method for step (1) described separation of solid and liquid is any one in sedimentation, filtering or centrifugation or at least two
Combination.
9. preparation method according to claim 7 or 8, which is characterized in that step (2) described catalyst is alkali；
Preferably, the alkali be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or triethylamine in any one or at least
Two kinds of combination；
Preferably, the ratio between step (2) intermediate and the amount of substance of the catalyst are 1:1；
Preferably, step (2) described solvent includes methanol, ethyl alcohol, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, N, N- dimethyl formyls
In amine, dichloromethane or chloroform any one or at least two combination；
Preferably, the ratio between amount of substance of step (2) intermediate and epoxychloropropane is 1:(2~15)；
Preferably, the temperature of step (2) described reaction is 40~120 DEG C；
Preferably, the reaction time before the aqueous solution of step (2) the addition alkali is 2~5 hours；
Preferably, the reaction time after the aqueous solution of step (2) the addition alkali is 4~8 hours；
Preferably, the aqueous solution of step (2) described alkali is sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution；
Preferably, the mass fraction of alkali is 30%~50% in the aqueous solution of step (2) described alkali；
Preferably, in the aqueous solution of step (2) described alkali the ratio between amount of substance of the addition of alkali and the intermediate for (3~
6):1；
Preferably, the method for step (2) described separation of solid and liquid is any one in sedimentation, filtering or centrifugation or at least two
Combination.
10. according to claim 7-9 any one of them preparation methods, which is characterized in that the described method comprises the following steps：
(1) according to molar ratio 1:(2~3) mix the compound containing A1 groups and the compound containing Y1 groups and solvent
It closes, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added after reacting 2~5 hour hour at 40~120 DEG C, 20
The reaction was continued at~50 DEG C 8~14 hour hour, and separation of solid and liquid obtains intermediate；
(2) intermediate and catalyst for obtaining equimolar step (1), with the 2 of solvent and the amount of the intermediate materials~
15 times of epoxychloropropane mixing, the aqueous solution of addition alkali after 2~5 hour hour react at 40~120 DEG C, and the reaction was continued 4~8
Hour hour, separation of solid and liquid obtain the phosphor-containing flame-proof type epoxy prepolymer.
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