CN109897167A - A kind of reactive flame retardant and its preparation method and application - Google Patents
A kind of reactive flame retardant and its preparation method and application Download PDFInfo
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- CN109897167A CN109897167A CN201711306097.9A CN201711306097A CN109897167A CN 109897167 A CN109897167 A CN 109897167A CN 201711306097 A CN201711306097 A CN 201711306097A CN 109897167 A CN109897167 A CN 109897167A
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Abstract
The present invention relates to a kind of reactive flame retardants and its preparation method and application, the composition epoxy resin that the reactive flame retardant substitution conventional curing agents are prepared, and the nylon composite being prepared as nylon fire retardant has good anti-flammability, good heat resistance, water resistance, mechanical performance and electrical property.The reactive flame retardant preparation cost of offer of the invention is cheap, raw material sources are abundant, properties are good, is with a wide range of applications.
Description
Technical field
The invention belongs to flame retardant area, it is related to a kind of reactive flame retardant and its preparation method and application.
Background technique
Using mobile phone, computer, video camera, electronic game machine as the electronic product of representative, with air-conditioning, refrigerator, television image, sound
The various products that articles etc. use for the household of representative, office electric equipment products and other field are rung, for safety, significant portion
Product require that it has anti-flammability and heat resistance.
Traditional technology generally uses addition aluminium hydroxide hydrate, magnesium hydroxide hydrate etc. into material system to contain
The inorganic fire-retarded substance such as the metal hydroxides of the crystallization water, and brominated bisphenol A, bmminated bisphenol-A type are added into material system
The method of the relatively high organic fire-resisting substance of the content of halogen such as epoxy resin makes product reach required flame retardant property or wait
Grade.In order to improve the anti-flammability for the organic chemicals that these contain halogen, such as antimony oxide is also usually added into system
Deng to the disagreeableness inorganic fire-retarded substance of environment.
Halogen-containing fire retardant matter can generate no degradability or noxious material difficult to degrade in burning, and (such as dioxin has
Machine halogen chemical substance), pollution environment influences the mankind and animal health.
Summary of the invention
For the technical problems in the prior art, the present invention provides a kind of reactive flame retardant and preparation method thereof,
The composition epoxy resin that the reactive flame retardant substitution conventional curing agents are prepared, and prepared as nylon fire retardant
Obtained nylon composite has good anti-flammability, good heat resistance, water resistance, mechanical performance.Offer of the invention
Reactive flame retardant preparation cost is cheap, raw material sources are abundant, properties are good, is with a wide range of applications.
In order to achieve the above objectives, the invention adopts the following technical scheme:
It is an object of the present invention to provide a kind of reactive flame retardant, the fire retardant has as shown in following formula I
Structure:
Wherein, R1 and R4 independently is hydrogen atom or meets any group of its chemical environment, and R2 is at least to contain one
The group of amino, R3 are to be not present or hydrogen atom or any group for meeting its chemical environment, R5 are Group VIA element or do not deposit
It is any one in oxygen atom, sulphur atom or nitrogen-atoms in, X, n is the positive integer more than or equal to 0；
Wherein,R' and R " are to meet its chemical environment
Any group, R6 and R7 are hydrogen atom or any group for meeting its chemical environment, and Y is in oxygen atom, sulphur atom or sulfuryl
Any one.
Wherein, described its chemical environment that meets is to refer to atom adjacent thereto to be connected, and obtains stable be connected chemically
Key.
Wherein, the amino can be primary amino group or secondary amino group.
As currently preferred technical solution, the R2 is the substituted or unsubstituted alkane at least containing an amino
It is base, substituted or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted
Aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl or substituted or unsubstituted alkane
Any one in base heteroaryl.
As currently preferred technical solution, the R1 and R4 are separately substituted or unsubstituted alkyl, take
It is generation or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted
Aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl, substituted or unsubstituted alkyl are miscellaneous
Aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryloxy group, substitution
Or unsubstituted alkoxy aryl, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy, substitution
Or unsubstituted alkyl heteroaryloxy, substituted or unsubstituted alkylamino, substituted or unsubstituted naphthene amino, replace or not
It is substituted fragrant amino, substituted or unsubstituted aryl alkane amino, substituted or unsubstituted alkyl fragrant amino, substituted or unsubstituted
It is heteroarylalkylamino, substituted or unsubstituted alkyl heteroaryl amino, substituted or unsubstituted alkyl thiol, substituted or unsubstituted
Aryl thiol, substituted or unsubstituted carboxylate, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group
Or any one in substituted or unsubstituted phosphonate group.
Preferably, R1 or R4 is separately and in Formulas IGroup is identical.
As currently preferred technical solution, the R3 is substituted or unsubstituted alkyl, substituted or unsubstituted ring
Alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryl alkyl, substitution
Or it is any in unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl or substituted or unsubstituted miscellaneous alkyl aryl
It is a kind of.
Wherein, when X is oxygen atom or sulphur atom, R3 is not present.
Wherein, when the phosphorus in Formulas I is trivalent, R5 is not present；The Group VIA element is appointing in oxygen, sulphur, selenium, tellurium or polonium
It anticipates one kind.
As currently preferred technical solution, the R6 and R7 are separately hydrogen atom or substituted or unsubstituted
Alkyl, substituted or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution or
Unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl or substitution do not take
Any one in the miscellaneous alkyl aryl in generation.
As currently preferred technical solution, the R' and R " are separately generation or unsubstituted linear chain or branched chain
Alkylidene, substituted or unsubstituted cycloalkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted sub- heteroaryl
It is base, substituted or unsubstituted arylidene alkylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted
Any one in alkylidene inferior heteroaryl or substituted or unsubstituted inferior heteroaryl alkylidene.
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 that C5~C13 (such as C6, C7, C8, C9, C10, C11 or C12) replaces
Or unsubstituted heteroaryl.
Substituted or unsubstituted alkylaryl be preferably C7~C13 (such as C8, C9, C10, C11 or C12) replace or
Unsubstituted alkylaryl.
Substituted or unsubstituted aryl alkyl be preferably C7~C13 (such as C8, C9, C10, C11 or C12) replace or
Unsubstituted alkylaryl.
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) replace or
Unsubstituted aryloxy group.
Substituted or unsubstituted alkoxy aryl is preferably C7~C12 (such as C8, C9, C10 or C11) substituted or unsubstituted
Alkoxy aryl.
Substituted or unsubstituted heteroarylalkoxy be preferably C7~C13 (such as C8, C9, C10, C11 or C12) replace or
Unsubstituted heteroarylalkoxy.
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) replace or
Unsubstituted fragrant amino.
Substituted or unsubstituted aryl alkane amino is preferably C7~C12 (such as C8, C9, C10 or C11) substituted or unsubstituted
Aryl alkane amino.
Substituted or unsubstituted heteroarylalkylamino be preferably C7~C13 (such as C8, C9, C10, C11 or C12) replace or
Unsubstituted heteroarylalkylamino.
Substituted or unsubstituted straight-chain alkyl-sub be preferably C1~C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) straight-chain alkyl-sub.
Substituted or unsubstituted branched alkylidene be preferably C1~C12 (such as C2, C3, C4, C5, C6, C7, C8, C9,
C10 or C11) branched alkylidene.
Substituted or unsubstituted arlydene is preferably the arlydene of C6~C13 (such as C7, C8, C9, C10, C11 or C12).
Substituted or unsubstituted inferior heteroaryl is preferably that C5~C13 (such as C6, C7, C8, C9, C10, C11 or C12) takes
Generation or unsubstituted inferior heteroaryl.
Substituted or unsubstituted alkylenearylene is preferably that C7~C13 (such as C8, C9, C10, C11 or C12) replaces
Or unsubstituted alkylenearylene.
Substituted or unsubstituted arylidene alkylene is preferably that C7~C13 (such as C8, C9, C10, C11 or C12) replaces
Or unsubstituted alkylenearylene.
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) replace or
Unsubstituted aryl thiol.
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) replace or do not take
Generation it is phosphate-based.
Substituted or unsubstituted alkyl acyl is preferably the alkyl acyl of C1~C6 (such as C2, C3, C4, C5 or C6).
Substituted or unsubstituted aryl-acyl is preferably the aryl acyl of C7~C13 (such as C8, C9, C10, C11 or C12)
Base.
In structure of the invention Formulas I, n is positive integer more than or equal to 0, n can be 0,1,2,3,4,5,6,7,8,9,10,
20,50 or 100 etc., it is not limited to cited numerical value, other interior unlisted numerical value of above-mentioned each numberical range are equally suitable
With.
Term " substituted " used in the present invention refers to that any one or more hydrogen atoms on specified atom are selected from
The substituent group of designated groups replaces, and condition is that the specified atom is no more than normal valency, and replaces the result is that generating stabilization
Compound.When substituent group is oxo group or ketone group (i.e.=O), then 2 hydrogen atoms on atom are substituted.Ketone replaces
Base is not present on aromatic rings." stable compound " be refer to it is sufficiently strong strongly from reaction mixture separation to effective
Purity is simultaneously configured to compounds effective.
The second purpose of the present invention is to provide a kind of preparation methods of above-mentioned reactive flame retardant, and the method includes following
Step:
Optionally, by P source compound withCopolymerization and reaction, are contained
Phosphorus dimer, oligomer or polymer；By P source compound or phosphorous dimer, oligomer or the polymer being prepared
Reactive flame retardant is obtained with the organic compound reaction containing at least one hydroxyl；
Wherein, phosphorus source compound include the chloride of phosphorus, the oxygenatedchemicals of phosphorus, halogenated phosphorous oxides, substitution or
In unsubstituted phosphate or substituted or unsubstituted phosphite ester any one or at least two combination；Y be oxygen atom,
Any one in sulphur atom or sulfuryl.
Wherein, the combination of phosphorus source compound is typical but non-limiting example has: the chloride of phosphorus and containing for phosphorus aoxidize
Close combination, halogenated phosphorous oxides and the substituted or unsubstituted phosphorus of the combination of object, the oxygenatedchemicals and halogenated phosphorous oxides of phosphorus
The combination of acid esters, substituted or unsubstituted phosphate and replace the combination of unsubstituted phosphite ester or the chloride of phosphorus, phosphorus
Oxygenatedchemicals and the combination of halogenated phosphorous oxides etc..
When P source compound be phosphorus chloride or halogenated phosphorous oxides when, in addition toOrCopolymerization and reaction are outer, in order to eliminate halogen atom, nucleopilic reagent can also be added and replace in P source compound
Halogen atom, have reached the purpose of halogen-free flameproof.
Wherein, the nucleopilic reagent can be substitution or for substituted sodium alkyl alcohol, substituted or unsubstituted fragrant phenol sodium,
Substitution is substituted lithium alkylide or grignard reagent etc., such as sodium methoxide, sodium ethoxide, sodium phenate, p-methyl phenol sodium, betanaphthol sodium
Or tert-butyl lithium etc..
The three of the object of the invention are to provide a kind of application of above-mentioned reactive flame retardant, and the reactive flame retardant is used for
Prepare composite material.
The present invention provides a kind of application of above-mentioned reactive flame retardant, and the reactive flame retardant is used for epoxy resin cure
Agent.
The present invention provides a kind of application of above-mentioned reactive flame retardant, and the reactive flame retardant is used for nylon fire retardant.
Compared with prior art, the present invention at least has the advantages that
(1) present invention provides a kind of reactive flame retardant, and it is solid that the reactive flame retardant can substitute epoxy resin completely
Agent, property of the composition epoxy resin being prepared better than the composition epoxy resin that conventional curing agents addition is prepared
Energy；
(2) present invention provides a kind of reactive flame retardant, the nylon composite tool that the reactive flame retardant is prepared
There is excellent mechanical performance, compression strength is up to 237MPa, and for tensile strength up to 177MPa, notched Izod impact hit intensity is reachable
35.9kJ/m2；
(3) present invention provides a kind of reactive flame retardant, and the reactive flame retardant synthesis cost is low, preparation method is simple
Single, raw material sources enrich, and are with a wide range of applications.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
The structure of the reactive flame retardant of the present embodiment is as follows:
The reactive flame retardant the preparation method is as follows:
2mol dichlorophenyl phosphine is put into three mouthfuls of 2000ml glass reactors with agitating device, 200mL acetone is passed through
Nitrogen, 1mol ethylene glycol disodium is added dropwise in 30min under stiring, continues to react at room temperature 60min, then 2mol ethylenediamine, 1g is added dropwise
DMAP continues to react at room temperature 120min, is washed to neutrality after reaction, with the impurity and moisture in physical method removal system, steams
The solvent in system is removed in distillation, obtains the reactive flame retardant 173.35g of above structure.
1H NMR(CDCl3, 500MHz): δ 7.40~7.26 (m, 10H, Ar-H), 3.95~3.88 (t, 4H, CH2), 2.76
~2.67 (m, 8H, CH2), 2.25~2.18 (t, 4H, NH2), 2.12~2.06 (t, 2H, NH).
Embodiment 2
The structure of the reactive flame retardant of the present embodiment is as follows:
The reactive flame retardant the preparation method is as follows:
2mol phosphorus trichloride is put into three mouthfuls of 2000ml glass reactors with agitating device, 200mL acetone is passed through nitrogen
Gas, 1mol hydroquinone disodium is added dropwise in 30min under stiring, continues to react at room temperature 60min, then 4mol ethylenediamine, 1g is added dropwise
DMAP continues to react at room temperature 120min, is washed to neutrality after reaction, with the impurity and moisture in physical method removal system, steams
The solvent in system is removed in distillation, obtains the reactive flame retardant 198.57g of above structure.
1H NMR(CDCl3, 500MHz): δ 6.96~6.72 (m, 4H, Ar-H), 2.77~2.62 (m, 16H, CH2), 2.26
~2.19 (t, 8H, NH2), 2.16~2.10 (t, 4H, NH).
Embodiment 3
The structure of the reactive flame retardant of the present embodiment is as follows:
The reactive flame retardant the preparation method is as follows:
2mol phosphorus oxychloride is put into three mouthfuls of 2000ml glass reactors with agitating device, 200mL acetone is passed through nitrogen
Gas, 1mol is added dropwise to Isosorbide-5-Nitrae-cyclohexanediol disodium in 30min under stiring, continues to react at room temperature 60min, then 4mol second two is added dropwise
Amine, 1g DMAP continue to react at room temperature 120min, neutrality are washed to after reaction, with the impurity and water in physical method removal system
Point, the solvent in system is distilled off, obtains the reactive flame retardant 240.86g of above structure.
1H NMR(CDCl3, 500MHz): δ 7.80~7.65 (m, 4H, PONH), 4.12~4.06 (m, 2H, CH), 3.87~
3.79 (m, 8H, CH2), 2.32~2.25 (m, 8H, CH2), 2.18~2.10 (t, 8H, NH2), 1.45~1.32 (m, 8H, CH2)。
Embodiment 4
The structure of the reactive flame retardant of the present embodiment is as follows:
The reactive flame retardant the preparation method is as follows:
Investment 2mol tert-butyl dichloro phosphoric acid in three mouthfuls of 2000ml glass reactors with agitating device, 200mL ethyl alcohol,
1mol Putriscine, 0.1mol sodium hydroxide, 0.1gDMAP are warming up to alcohol reflux, stir lower reaction 8h, add
2mol Isosorbide-5-Nitrae-cyclohexanediamine reacts 2h, neutrality is washed to after reaction, with the impurity and water in physical method removal system
Point, the solvent in system is distilled off, obtains the reactive flame retardant 249.22g of above structure.
1H NMR(CDCl3, 500MHz): δ 7.82~7.63 (m, 4H, PONH), 4.52~4.46 (m, 4H, CH2), 3.85
~3.80 (m, 2H, CH), 2.36~2.29 (m, 2H, CH), 1.60~1.55 (m, 4H, CH2), 1.51~1.38 (m, 16H,
CH2), 0.91~0.87 (s, 18H, CH3)。
Embodiment 5
The structure of the reactive flame retardant of the present embodiment is as follows:
1.1mol trimethyl phosphate is put into three mouthfuls of 2000ml glass reactors with agitating device, 200mL acetone leads to
Entering nitrogen, 1mol Isosorbide-5-Nitrae-dibenzylamine is added dropwise in 30min under stiring, and 1g DMAP is warming up to acetone reflux, lower reaction 2h is stirred,
It is washed to neutrality after reaction, with the impurity and moisture in physical method removal system, the solvent in system is distilled off, obtains
To the reactive flame retardant 205.31g of above structure.
1H NMR(CDCl3, 500MHz): δ 7.82~7.75 (t, H, PONH), 7.17~7.08 (t, 4H, Ar-H), 4.45
~4.37 (d, 2H, CH2), 3.52~3.44 (t, 2H, CH2), 3.27~3.22 (s, 6H, CH3), 2.18~2.10 (t, 2H,
NH2)。
Embodiment 6
The structure of the reactive flame retardant of the present embodiment is as follows:
4mol phosphoric acid egg methyl esters is put into three mouthfuls of 5000ml glass reactors with agitating device, 200mL acetone is passed through
4mol 1,6- hexamethylene diamine is added in nitrogen, and 5g DMAP is warming up to acetone reflux, stirs lower reaction 6h, is washed to after reaction
The solvent in system is distilled off with the impurity and moisture in physical method removal system in neutrality, obtains the reaction of above structure
Sex flame retardant 357.62g.
1H NMR(CDCl3, 500MHz): δ 7.77~7.65 (t, H, PONH), 4.25~4.16 (t, 2H, CH2), 2.84~
2.75 (t, 2H, CH2), 2.37~2.31 (s, 3H, CH3), 2.17~2.10 (m, H, NH), 1.23~1.12 (m, 8H, CH2),
0.97~0.87 (s, 3H, CH3)。
Embodiment 7
In the present embodiment, 40 parts by weight of reactive flame retardant that embodiment 1 are prepared, epoxide equivalent 186g/
100 parts of the liquid bisphenol A epoxy resin of eq, 60 parts of methyl tetrahydro phthalic anhydride, 0.5 parts by weight of 2-methylimidazole and silica 90
Composition epoxy resin x is obtained after parts by weight mixing.
Embodiment 8
In the present embodiment, 100 parts by weight of reactive flame retardant that embodiment 1 are prepared, epoxide equivalent 186g/
It is obtained after 100 parts of the liquid bisphenol A epoxy resin of eq, 0.5 parts by weight of 2-methylimidazole and the mixing of 90 parts by weight of silica
Composition epoxy resin a.
Embodiment 9
In the present embodiment, 100 parts by weight of reactive flame retardant that embodiment 2 are prepared, epoxide equivalent 186g/
It is obtained after 100 parts of the liquid bisphenol A epoxy resin of eq, 0.5 parts by weight of 2-methylimidazole and the mixing of 90 parts by weight of silica
Composition epoxy resin b.
Embodiment 10
In the present embodiment, 105 parts by weight of reactive flame retardant embodiment 3 being prepared, epoxide equivalent 195g/
It is obtained after 100 parts of the o-cresol formaldehyde epoxy resin of eq, 0.5 parts by weight of 2-methylimidazole and the mixing of 90 parts by weight of silica
Composition epoxy resin c.
Embodiment 11
In the present embodiment, 110 parts by weight of reactive flame retardant embodiment 4 being prepared, epoxide equivalent 195g/
It is obtained after 100 parts of the o-cresol formaldehyde epoxy resin of eq, 0.5 parts by weight of 2-methylimidazole and the mixing of 90 parts by weight of silica
Composition epoxy resin d.
Embodiment 12
In the present embodiment, 110 parts by weight of reactive flame retardant embodiment 5 being prepared, epoxide equivalent 195g/
It is obtained after 100 parts of the o-cresol formaldehyde epoxy resin of eq, 0.5 parts by weight of 2-methylimidazole and the mixing of 90 parts by weight of silica
Composition epoxy resin e.
Embodiment 13
In the present embodiment, 100 parts by weight of reactive flame retardant embodiment 6 being prepared, epoxide equivalent 195g/
It is obtained after 100 parts of the o-cresol formaldehyde epoxy resin of eq, 0.5 parts by weight of 2-methylimidazole and the mixing of 90 parts by weight of silica
Composition epoxy resin f.
The performance of the embodiment 7-13 composition epoxy resin being prepared is measured, the results are shown in Table 1.
Table 1
From table 2 it can be seen that the reactive flame retardant substitution being prepared using 1-6 of the embodiment of the present invention was originally used
The performance for the acrylic acid resin composition that anhydride curing agent is prepared is approximate with embodiment 7.
Embodiment 14
In the present embodiment, 25 parts by weight of reactive flame retardant embodiment 1 being prepared, with 81 weight of nylon 610
Part, 23 parts by weight of nylon66 fiber, 0.7 parts by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, antioxidant 1010
0.8 parts by weight of 0.6 parts by weight, 34 parts by weight of glass fibre and double stearic amides, are mixed with to obtain nylon composite materials
a。
Embodiment 15
In the present embodiment, 30 parts by weight of reactive flame retardant embodiment 2 being prepared, with 81 weight of nylon 610
Part, 23 parts by weight of nylon66 fiber, 0.7 parts by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, antioxidant 1010
0.8 parts by weight of 0.6 parts by weight, 34 parts by weight of glass fibre and double stearic amides, are mixed with to obtain nylon composite materials
b。
Embodiment 16
In the present embodiment, 35 parts by weight of reactive flame retardant embodiment 3 being prepared, with 81 weight of nylon 610
Part, 23 parts by weight of nylon66 fiber, 0.7 parts by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, antioxidant 1010
0.8 parts by weight of 0.6 parts by weight, 34 parts by weight of glass fibre and double stearic amides, are mixed with to obtain nylon composite materials
c。
Embodiment 17
In the present embodiment, 35 parts by weight of reactive flame retardant embodiment 4 being prepared, with 81 weight of nylon 610
Part, 23 parts by weight of nylon66 fiber, 0.7 parts by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, antioxidant 1010
0.8 parts by weight of 0.6 parts by weight, 34 parts by weight of glass fibre and double stearic amides, are mixed with to obtain nylon composite materials
d。
Embodiment 18
In the present embodiment, 30 parts by weight of reactive flame retardant embodiment 5 being prepared, with 81 weight of nylon 610
Part, 23 parts by weight of nylon66 fiber, 0.7 parts by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, antioxidant 1010
0.8 parts by weight of 0.6 parts by weight, 34 parts by weight of glass fibre and double stearic amides, are mixed with to obtain nylon composite materials
e。
Embodiment 19
In the present embodiment, 30 parts by weight of reactive flame retardant embodiment 6 being prepared, with 81 weight of nylon 610
Part, 23 parts by weight of nylon66 fiber, 0.7 parts by weight of vinyltriethoxysilane, 12 parts by weight of magnesium hydroxide, antioxidant 1010
0.8 parts by weight of 0.6 parts by weight, 34 parts by weight of glass fibre and double stearic amides, are mixed with to obtain nylon composite materials
f。
Comparative example 1
In this comparative example, 30 parts by weight of reactive flame retardant that embodiment 1 is prepared are replaced with into benzenediol tetraphenyl
30 parts by weight of bisphosphate, other conditions are identical as embodiment 14, are mixed with to obtain nylon composite materials g.
To the compression strength of embodiment 14-19 and comparative example 1 nylon composite materials being prepared, tensile strength, lack
Mouth impact strength and flammability are tested, and the results are shown in Table 2.
Table 2
From table 2 it can be seen that the nylon being prepared using the reactive flame retardant that 1-6 of the embodiment of the present invention is prepared
The performance of composite material is better than comparative example 1 comprehensively.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of reactive flame retardant, which is characterized in that the fire retardant has the structure as shown in following formula I:
Wherein, R1 and R4 independently is hydrogen atom or meets any group of its chemical environment, and R2 is to contain at least one amino
Group, R3 is to be not present or hydrogen atom or any group for meeting its chemical environment, R5 are Group VIA element or are not present that X is
Any one in oxygen atom, sulphur atom or nitrogen-atoms, n are the positive integer more than or equal to 0；
Wherein, R isR' and R " are to meet any of its chemical environment
Group, R6 and R7 are hydrogen atom or any group for meeting its chemical environment, and Y is any in oxygen atom, sulphur atom or sulfuryl
It is a kind of.
2. fire retardant according to claim 1, which is characterized in that the R2 is for the substitution containing at least one amino or not
Substituted alkyl, substituted or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution
Or unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl or substitution or not
Any one in substituted miscellaneous alkyl aryl.
3. fire retardant according to claim 1 or 2, which is characterized in that the R1 and R4 separately be replace or not
Substituted alkyl, substituted or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl,
Substituted or unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl, substitution or
Unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, replace or it is unsubstituted
Aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroaryl
Base alkoxy, substituted or unsubstituted alkyl heteroaryloxy, substituted or unsubstituted alkylamino, substituted or unsubstituted cycloalkanes ammonia
Base, substituted or unsubstituted fragrant amino, substituted or unsubstituted aryl alkane amino, substituted or unsubstituted alkyl fragrant amino,
Substituted or unsubstituted heteroarylalkylamino, substituted or unsubstituted alkyl heteroaryl amino, substituted or unsubstituted alkyl thiol,
Substituted or unsubstituted aryl thiol, substituted or unsubstituted carboxylate, substituted or unsubstituted carbonate group, substitution or not
Any one in substituted sulfonate group or substituted or unsubstituted phosphonate group；
Preferably, R1 or R4 is separately and in Formulas IGroup is identical.
4. fire retardant according to claim 1-3, which is characterized in that the R3 is substituted or unsubstituted alkane
It is base, substituted or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted
Aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl or substituted or unsubstituted alkane
Any one in base heteroaryl.
5. fire retardant according to claim 1-4, which is characterized in that the R6 and R7 is separately hydrogen original
It is sub or substituted or unsubstituted alkyl, substituted or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted
Heteroaryl, substituted or unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl
Or any one in substituted or unsubstituted miscellaneous alkyl aryl.
6. fire retardant according to claim 1-5, the R' and R " are separately substituted or unsubstituted
Linear chain or branched chain alkylidene, substituted or unsubstituted cycloalkylidene, substituted or unsubstituted arlydene, replace or do not take
The inferior heteroaryl in generation, substituted or unsubstituted arylidene alkylene, substituted or unsubstituted alkylenearylene, replace
Or any one in unsubstituted alkylidene inferior heteroaryl or substituted or unsubstituted inferior heteroaryl alkylidene.
7. a kind of preparation method of reactive flame retardant described in any one of claims 1-6, which is characterized in that the method packet
Include following steps:
Optionally, by P source compound withOr HY-R "-YH is copolymerized and reaction, obtains phosphorous dimer, oligomerization
Body or polymer；By P source compound or phosphorous dimer, oligomer or the polymer being prepared with contain at least one
The organic compound reaction of a amino obtains reactive flame retardant；
Wherein, phosphorus source compound includes the chloride of phosphorus, the oxygenatedchemicals of phosphorus, halogenated phosphorous oxides, substitution or does not take
In the phosphate in generation or substituted or unsubstituted phosphite ester any one or at least two combination；Y is oxygen atom, sulphur original
Son or sulfuryl in any one.
8. a kind of application of reactive flame retardant described in any one of claims 1-6, which is characterized in that the reactivity is fire-retardant
Agent is used to prepare composite material.
9. a kind of application of reactive flame retardant described in any one of claims 1-6, which is characterized in that the reactivity is fire-retardant
Agent is used for epoxy curing agent.
10. a kind of application of reactive flame retardant described in any one of claims 1-6, which is characterized in that the reactivity resistance
It fires agent and is used for nylon fire retardant.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442069A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with amido, preparation method and application thereof |
| CN112480657A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Polyamide resin composition and preparation method and application thereof |
| CN112480371A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Epoxy resin composition and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101460511A (en) * | 2006-06-09 | 2009-06-17 | 昭和高分子株式会社 | Process for production of aminated phosphoric acid ester compound, flame-retardant resin, and flame-retardant resin composition |
| CN101870870A (en) * | 2010-06-11 | 2010-10-27 | 天津工业大学 | Phosphonate flame retardant and preparation method thereof |
| CN102432837A (en) * | 2011-10-12 | 2012-05-02 | 上海交通大学 | Phosphor and nitrogen containing flame retardant curing agent, preparation method and application thereof |
| CN105273122A (en) * | 2015-04-16 | 2016-01-27 | 刘义林 | Flame-retardant modified polyvinyl acetate emulsion and preparation method therefor |
| CN105924626A (en) * | 2016-06-24 | 2016-09-07 | 长春工业大学 | Liquid colorless and transparent epoxy resin halogen-free flame retardant curing agent and preparation method thereof |
| CN106117515A (en) * | 2016-07-13 | 2016-11-16 | 沈阳化工大学 | A kind of phosphorous, azo-cycle epoxy resins flame retardant curing agent and preparation method thereof |
-
2017
- 2017-12-11 CN CN201711306097.9A patent/CN109897167A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101460511A (en) * | 2006-06-09 | 2009-06-17 | 昭和高分子株式会社 | Process for production of aminated phosphoric acid ester compound, flame-retardant resin, and flame-retardant resin composition |
| CN101870870A (en) * | 2010-06-11 | 2010-10-27 | 天津工业大学 | Phosphonate flame retardant and preparation method thereof |
| CN102432837A (en) * | 2011-10-12 | 2012-05-02 | 上海交通大学 | Phosphor and nitrogen containing flame retardant curing agent, preparation method and application thereof |
| CN105273122A (en) * | 2015-04-16 | 2016-01-27 | 刘义林 | Flame-retardant modified polyvinyl acetate emulsion and preparation method therefor |
| CN105924626A (en) * | 2016-06-24 | 2016-09-07 | 长春工业大学 | Liquid colorless and transparent epoxy resin halogen-free flame retardant curing agent and preparation method thereof |
| CN106117515A (en) * | 2016-07-13 | 2016-11-16 | 沈阳化工大学 | A kind of phosphorous, azo-cycle epoxy resins flame retardant curing agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LIDONG ZHANG ET AL: "pH-reversible supramolecular hydrogels based on aminoalkyl phosphoamide compounds", 《SUPRAMOLECULAR CHEMISTRY》 * |
| WENYAN LYU ET AL: "Synthesis, thermal stability, and flame retardancy of PA66, treated with dichlorophenylphsophine derivatives", 《DESIGNED MONOMERS AND POLYMERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112442069A (en) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with amido, preparation method and application thereof |
| CN112480657A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Polyamide resin composition and preparation method and application thereof |
| CN112480371A (en) * | 2019-09-11 | 2021-03-12 | 广东广山新材料股份有限公司 | Epoxy resin composition and preparation method and application thereof |
| CN112480371B (en) * | 2019-09-11 | 2024-03-19 | 广东广山新材料股份有限公司 | Epoxy resin composition and preparation method and application thereof |
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