CN109897218A - 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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- CN109897218A CN109897218A CN201711307069.9A CN201711307069A CN109897218A CN 109897218 A CN109897218 A CN 109897218A CN 201711307069 A CN201711307069 A CN 201711307069A CN 109897218 A CN109897218 A CN 109897218A
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Abstract
The present invention provides a kind of reactive flame retardant and its preparation method and application, moulding material, unsaturated resin composition and the glass reinforced plastic that the reactive flame retardant is prepared have 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.
The non-halogen flame-retardant cable of the prior art causes because of addition organophosphorus ester and/or phosphorus nitrogen expansion type flame-retardant system
The disadvantages such as mechanical performance declines to a great extent, and flame retardant rating is low, and temperature resistant grade is low.
Summary of the invention
For the technical problems in the prior art, the present invention provide a kind of reactive flame retardant have it is excellent fire-retardant
Performance, without smoke, can be applied in the fields such as moulding material, unsaturated resin composition and glass reinforced plastic, insatiable hunger can not only be improved
With the fire-retardant and heat resistance of the materials such as resin combination and glass reinforced plastic, moreover it is possible to improve the mechanical performance and water resistance of above-mentioned material
Can, the quality of material is improved comprehensively.
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 containing substituted or not
The group of substituted unsaturated alkyl or at least one of substituted or unsubstituted unsaturated ring alkyl, R3 are to be not present or hydrogen is former
Son or any group for meeting its chemical environment, R5 are Group VIA element or are not present that X is in oxygen atom, sulphur atom or nitrogen-atoms
Any one, n is positive integer more than or equal to 0；
Wherein, R isR' 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, substituted or unsubstituted unsaturated alkyl be preferably C1~C12 (such as C2, C3, C4, C5, C6, C7, C8,
C9, C10 or C11) unsaturated alkyl；Substituted or unsubstituted unsaturated ring alkyl be preferably C3~C12 (such as C4, C5,
C6, C7, C8, C9, C10 or C11) unsaturated ring alkyl；Unsaturated bond in the unsaturated alkyl and unsaturated ring alkyl
For carbon-carbon double bond and/or triple carbon-carbon bonds.
Wherein, described its chemical environment that meets is to refer to atom adjacent thereto to be connected, and obtains stable be connected chemically
Key.
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, the R3 be substituted or unsubstituted alkyl, substituted or unsubstituted naphthenic base, replace or it is unsubstituted
Aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl,
Any one in substituted or unsubstituted heteroaryl alkyl or substituted or unsubstituted miscellaneous alkyl aryl.
Preferably, R1 or R4 is separately and in Formulas IGroup is identical.
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 do not take
The aryl alkyl in generation, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl or substituted or unsubstituted
Any one in miscellaneous alkyl aryl.
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 withOr HY-R "-YH copolymerization and reaction, obtain phosphorous dimer,
Oligomer or polymer；By P source compound or phosphorous dimer, oligomer or the polymer being prepared with containing taking
The organic compound reaction of generation or unsubstituted unsaturated alkyl or substituted or unsubstituted unsaturated ring alkyl obtains reactivity
Fire retardant；
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 toOr HY-R "-
YH copolymerization and reaction are outer, in order to eliminate halogen atom, the halogen atom in nucleopilic reagent substitution P source compound can also be added, 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 moulding material and composite material.
The present invention also provides a kind of application of above-mentioned reactive flame retardant, the reactive flame retardant is used to prepare unsaturation
Resin combination.
The present invention also provides a kind of application of above-mentioned reactive flame retardant, the reactive flame retardant is used to prepare glass
Steel.
Compared with prior art, the present invention at least has the advantages that
(1) present invention provides a kind of reactive flame retardant, the acrylic resin group that the reactive flame retardant is prepared
The mechanical performance for closing object is excellent, and compression strength is up to 37.9MPa, and for tensile strength up to 26.1MPa, excellent thermal insulation performance is thermally conductive
For coefficient down to 0.0115W/ (mK), water resistance is excellent, and tensile strength change is lower than 10% after water-fast test；
(2) present invention provides a kind of reactive flame retardant, the machinery for the glass reinforced plastic that the reactive flame retardant is prepared
Have excellent performance, compression strength is up to 302MPa, and tensile strength is up to 125MPa, excellent thermal insulation performance, thermal coefficient down to
0.0082W/ (mK), water resistance is excellent, and tensile strength change is lower than 10% after water-fast test；
(3) present invention provides a kind of reactive flame retardant, and the heat point of PE-PP wire rod is prepared in the reactive flame retardant
Temperature is solved up to 300 DEG C or more, tensile strength is up to 27.2MPa, and elongation at break is up to 233%, tension after water resistance test
Intensity is dropped by less than 10%, and flammability test is up to V-0 grade, with excellent mechanical performance, water resistance, heat resistance with
And flame retardant property；
(4) 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 propylene sodium alkoxide is added dropwise, after
Continuous room temperature reaction 120min, after reaction, with the impurity and moisture in physical method removal system, is distilled off molten in system
Agent obtains the reactive flame retardant 166.31g of above structure.
1H NMR(CDCl3, 500MHz): δ 7.32~7.16 (m, 10H, Ar-H), 5.88~5.80 (m, 2H, CH=
CH2), 5.32~5.24 (t, 4H, CH=CH 2), 4.05~3.97 (t, 4H, CH2), 3.91~3.86 (t, 4H, CH2)。
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 2- butylene sodium alkoxide is added dropwise,
Continue to react at room temperature 120min, after reaction, with the impurity and moisture in physical method removal system, be distilled off molten in system
Agent obtains the reactive flame retardant 201.93g of above structure.
1H NMR(CDCl3, 500MHz): δ 6.98~6.84 (m, 4H, Ar-H), 5.48~5.41 (m, 8H, CH=CH),
4.11~4.02 (t, 8H, CH2), 1.75~1.68 (t, 12H, CH3)。
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 propenyl is added dropwise
Sodium continues to react at room temperature 120min, after reaction, with the impurity and moisture in physical method removal system, be distilled off in system
Solvent, obtain the reactive flame retardant 245.60g of above structure.
1H NMR(CDCl3, 500MHz): δ 6.05~5.92 (d, 8H, CH2), 5.87~5.80 (m, 2H, CH=CH2),
5.33~5.26 (t, 4H, CH=CH 2), 4.12~4.06 (m, 2H, CH), 1.45~1.32 (m, 8H, CH2)。
Embodiment 4
The structure of the reactive flame retardant of the present embodiment 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-cyclopentadiene -3- sodium alkoxide continues to react at room temperature 120min, after reaction, with the impurity in physical method removal system
And moisture, the solvent in system is distilled off, obtains the reactive flame retardant 240.66g of above structure.
1H NMR(CDCl3, 500MHz): δ 7.82~7.63 (t, 2H, PONH), 6.88~6.82 (m, 2H, CH), 5.45
~5.37 (m, 8H, CH=CH), 4.51~4.45 (t, 4H, CH2), 0.95~0.89 (s, 18H, CH3), 1.42~1.32 (m,
4H, CH2)。
Embodiment 5
The structure of the reactive flame retardant of the present embodiment is as follows:
Investment 1.1mol trimethyl phosphate in three mouthfuls of 2000ml glass reactors with agitating device, 200mL ethyl alcohol,
1mol 4- vinyl benzyl amine, 0.1mol sodium hydroxide, 0.1gDMAP are warming up to alcohol reflux, stir lower reaction 8h, reaction knot
It is washed to neutrality after beam, with the impurity and moisture in physical method removal system, the solvent in system is distilled off, obtains above-mentioned
The reactive flame retardant 193.52g of structure.
1H NMR(CDCl3, 500MHz): δ 7.85~7.67 (t, H, PONH), 7.43~7.38 (t, 2H, Ar-H), 6.78
~6.72 (t, 2H, Ar-H), 6.65~6.62 (m, H, CH2=CH), 5.63~5.58 (t, H, CH 2=CH), 5.20~5.15
(t, H, CH 2=CH), 3.67~3.61 (d, 2H, CH2), 3.27~3.22 (s, 6H, CH3)。
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 Isosorbide-5-Nitrae-butylene glycol disodium is added in nitrogen, is warming up to acetone reflux, stirs lower reaction 6h, 5L is added dropwise after reaction
1mol/L hydrochloric acid, is washed to neutrality, and with the impurity and moisture in physical method removal system, the solvent in system is distilled off,
Obtain the reactive flame retardant 361.58g of above structure.
1H NMR(CDCl3, 500MHz): δ 5.47~5.40 (m, 4H, CH=CH), 5.33~5.26 (t, 2H, CH2),
3.91~3.85 (t, 2H, CH2), 3.27~3.22 (s, 3H, CH3)。
Embodiment 7
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 1, with 15 weight of methyl methacrylate
Part, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 parts by weight of methacrylic acid, hydroxypropyl acrylate 13
Parts by weight, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of dimethylbenzene, 20 weight of butanone
Amount part and 10 parts by weight of cyclohexanone are mixed with cross-linking type acrylic acid resin combination a.
Embodiment 8
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment, with 15 weight of methyl methacrylate
Part, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 parts by weight of methacrylic acid, hydroxypropyl acrylate 13
Parts by weight, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of dimethylbenzene, 20 weight of butanone
Amount part and 10 parts by weight of cyclohexanone are mixed with cross-linking type acrylic acid resin combination b.
Embodiment 9
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 3, with 15 weight of methyl methacrylate
Part, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 parts by weight of methacrylic acid, hydroxypropyl acrylate 13
Parts by weight, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of dimethylbenzene, 20 weight of butanone
Amount part and 10 parts by weight of cyclohexanone are mixed with cross-linking type acrylic acid resin combination c.
Embodiment 10
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 4, with 15 weight of methyl methacrylate
Part, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 parts by weight of methacrylic acid, hydroxypropyl acrylate 13
Parts by weight, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of dimethylbenzene, 20 weight of butanone
Amount part and 10 parts by weight of cyclohexanone are mixed with cross-linking type acrylic acid resin combination d.
Embodiment 11
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 5, with 15 weight of methyl methacrylate
Part, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 parts by weight of methacrylic acid, hydroxypropyl acrylate 13
Parts by weight, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of dimethylbenzene, 20 weight of butanone
Amount part and 10 parts by weight of cyclohexanone are mixed with cross-linking type acrylic acid resin combination e.
Embodiment 12
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 6, with 15 weight of methyl methacrylate
Part, 15 parts by weight of butyl methacrylate, 11 parts by weight of ethyl acrylate, 1 parts by weight of methacrylic acid, hydroxypropyl acrylate 13
Parts by weight, 45 parts by weight of trifluoroethyl methacrylate, 2 parts by weight of benzoyl peroxide, 70 parts by weight of dimethylbenzene, 20 weight of butanone
Amount part and 10 parts by weight of cyclohexanone are mixed with cross-linking type acrylic acid resin combination f.
Comparative example 1
In this comparative example, 50 parts by weight of reactive flame retardant prepared by embodiment 1 are replaced with into 50 weight of triphenyl phosphate
Part, other conditions are same as Example 7, are mixed with cross-linking type acrylic acid resin combination g.
To the compression strength of embodiment 7-12 and comparative example 1 acrylic acid resin composition being prepared, tensile strength,
Thermal coefficient, water resistance and flammability are tested, and the results are shown in Table 1.Water resistance is will be after intensity test
Polyurethane leather be soaked in 25 DEG C of water for 24 hours after, carry out intensity test again.
Table 1
As it can be seen from table 1 the propylene being prepared using the reactive flame retardant that 1-6 of the embodiment of the present invention is prepared
The performance of acid resin composition is better than comparative example 1 comprehensively.
Embodiment 13
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 1, with bisphenol A-type unsaturated polyester (UP) tree
20 parts of 50 parts by weight of rouge, polyvinyl acetate and polymethylmethacrylablock block copolymer, 1 parts by weight of cobalt iso-octoate, peroxide
Change 0.5 parts by weight of dibenzoyl, 2 parts by weight of methyl ethyl ketone peroxide, 0.15 parts by weight of light magnesium oxide, 100 weight of Strong oxdiative aluminium
Simultaneously intermediate temperature setting prepares glass reinforced plastic a for part, 2 parts by weight of zinc stearate and the mixing of 100 parts by weight of glass fibre.
Embodiment 14
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 2, with bisphenol A-type unsaturated polyester (UP) tree
20 parts of 50 parts by weight of rouge, polyvinyl acetate and polymethylmethacrylablock block copolymer, 1 parts by weight of cobalt iso-octoate, peroxide
Change 0.5 parts by weight of dibenzoyl, 2 parts by weight of methyl ethyl ketone peroxide, 0.15 parts by weight of light magnesium oxide, 100 weight of Strong oxdiative aluminium
Simultaneously intermediate temperature setting prepares glass reinforced plastic b for part, 2 parts by weight of zinc stearate and the mixing of 100 parts by weight of glass fibre.
Embodiment 15
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 3, with bisphenol A-type unsaturated polyester (UP) tree
20 parts of 50 parts by weight of rouge, polyvinyl acetate and polymethylmethacrylablock block copolymer, 1 parts by weight of cobalt iso-octoate, peroxide
Change 0.5 parts by weight of dibenzoyl, 2 parts by weight of methyl ethyl ketone peroxide, 0.15 parts by weight of light magnesium oxide, 100 weight of Strong oxdiative aluminium
Simultaneously intermediate temperature setting prepares glass reinforced plastic c for part, 2 parts by weight of zinc stearate and the mixing of 100 parts by weight of glass fibre.
Embodiment 16
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 4, with bisphenol A-type unsaturated polyester (UP) tree
20 parts of 50 parts by weight of rouge, polyvinyl acetate and polymethylmethacrylablock block copolymer, 1 parts by weight of cobalt iso-octoate, peroxide
Change 0.5 parts by weight of dibenzoyl, 2 parts by weight of methyl ethyl ketone peroxide, 0.15 parts by weight of light magnesium oxide, 100 weight of Strong oxdiative aluminium
Simultaneously intermediate temperature setting prepares glass reinforced plastic d for part, 2 parts by weight of zinc stearate and the mixing of 100 parts by weight of glass fibre.
Embodiment 17
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 5, with bisphenol A-type unsaturated polyester (UP) tree
20 parts of 50 parts by weight of rouge, polyvinyl acetate and polymethylmethacrylablock block copolymer, 1 parts by weight of cobalt iso-octoate, peroxide
Change 0.5 parts by weight of dibenzoyl, 2 parts by weight of methyl ethyl ketone peroxide, 0.15 parts by weight of light magnesium oxide, 100 weight of Strong oxdiative aluminium
Simultaneously intermediate temperature setting prepares glass reinforced plastic e for part, 2 parts by weight of zinc stearate and the mixing of 100 parts by weight of glass fibre.
Embodiment 18
In the present embodiment, 50 parts by weight of reactive flame retardant prepared by embodiment 6, with bisphenol A-type unsaturated polyester (UP) tree
20 parts of 50 parts by weight of rouge, polyvinyl acetate and polymethylmethacrylablock block copolymer, 1 parts by weight of cobalt iso-octoate, peroxide
Change 0.5 parts by weight of dibenzoyl, 2 parts by weight of methyl ethyl ketone peroxide, 0.15 parts by weight of light magnesium oxide, 100 weight of Strong oxdiative aluminium
Simultaneously intermediate temperature setting prepares glass reinforced plastic f for part, 2 parts by weight of zinc stearate and the mixing of 100 parts by weight of glass fibre.
Comparative example 2
In this comparative example, 50 parts by weight of reactive flame retardant prepared by embodiment 1 are replaced with into dimethyl methyl phosphonate 50
Part, other conditions are identical as embodiment 13, mix and intermediate temperature setting prepares glass reinforced plastic g.
To the compression strength of embodiment 13-18 and comparative example 2 glass reinforced plastic being prepared, tensile strength, thermal coefficient,
Dimensional stability and flammability are tested, and the results are shown in Table 2.
Table 2
From table 2 it can be seen that the glass being prepared using the reactive flame retardant that 1-6 of the embodiment of the present invention is prepared
The performance of steel is better than comparative example 2 comprehensively.
Embodiment 19
In the present embodiment, 35 parts by weight of reactive flame retardant prepared by embodiment 1, with 20 weight of ethylene-propylene copolymer
Measure part, pungent dilute 5 parts by weight of copolymer of ethylene-, 30 parts by weight of polyethylene, 45 parts by weight of polypropylene, ethylene-ethylacrylate copolymerization
3 parts by weight melt blending of 10 parts by weight of object, 3 parts by weight of calcium stearate and silicone master batch, extrusion obtain PE-PP wire rod a.
Embodiment 20
In the present embodiment, 35 parts by weight of reactive flame retardant prepared by embodiment 2, with 20 weight of ethylene-propylene copolymer
Measure part, pungent dilute 5 parts by weight of copolymer of ethylene-, 30 parts by weight of polyethylene, 45 parts by weight of polypropylene, ethylene-ethylacrylate copolymerization
3 parts by weight melt blending of 10 parts by weight of object, 3 parts by weight of calcium stearate and silicone master batch, extrusion obtain PE-PP wire rod b.
Embodiment 21
In the present embodiment, 35 parts by weight of reactive flame retardant prepared by embodiment 3, with 20 weight of ethylene-propylene copolymer
Measure part, pungent dilute 5 parts by weight of copolymer of ethylene-, 30 parts by weight of polyethylene, 45 parts by weight of polypropylene, ethylene-ethylacrylate copolymerization
3 parts by weight melt blending of 10 parts by weight of object, 3 parts by weight of calcium stearate and silicone master batch, extrusion obtain PE-PP wire rod c.
Embodiment 22
In the present embodiment, 35 parts by weight of reactive flame retardant prepared by embodiment 4, with 20 weight of ethylene-propylene copolymer
Measure part, pungent dilute 5 parts by weight of copolymer of ethylene-, 30 parts by weight of polyethylene, 45 parts by weight of polypropylene, ethylene-ethylacrylate copolymerization
3 parts by weight melt blending of 10 parts by weight of object, 3 parts by weight of calcium stearate and silicone master batch, extrusion obtain PE-PP wire rod d.
Embodiment 23
In the present embodiment, 35 parts by weight of reactive flame retardant prepared by embodiment 5, with 20 weight of ethylene-propylene copolymer
Measure part, pungent dilute 5 parts by weight of copolymer of ethylene-, 30 parts by weight of polyethylene, 45 parts by weight of polypropylene, ethylene-ethylacrylate copolymerization
3 parts by weight melt blending of 10 parts by weight of object, 3 parts by weight of calcium stearate and silicone master batch, extrusion obtain PE-PP wire rod e.
Embodiment 24
In the present embodiment, 35 parts by weight of reactive flame retardant prepared by embodiment 6, with 20 weight of ethylene-propylene copolymer
Measure part, pungent dilute 5 parts by weight of copolymer of ethylene-, 30 parts by weight of polyethylene, 45 parts by weight of polypropylene, ethylene-ethylacrylate copolymerization
3 parts by weight melt blending of 10 parts by weight of object, 3 parts by weight of calcium stearate and silicone master batch, extrusion obtain PE-PP wire rod f.
Comparative example 3
In this comparative example, 35 parts by weight of reactive flame retardant prepared by embodiment 1 are replaced with into 35 parts by weight of ammonium polyphosphate
Outside, other conditions are identical as embodiment 19, and melt blending squeezes out to obtain PE-PP wire rod g.
To the mechanical performance of the obtained PE-PP wire rod of embodiment 19-24 and comparative example 3, water resistance, heat resistance with
And flame retardant property is tested, the results are shown in Table 3.Wherein embodiment and comparative example are prepared water resistance test
PE-PP wire rod carries out the obtained result of tensile strength test after impregnating 7 days in 25 DEG C of water after tensile strength test again.
Table 3
The heat that PE-PP wire rod is prepared in reactive flame retardant described in 1-6 of the embodiment of the present invention is added as can be seen from Table 3
Decomposition temperature is up to 300 DEG C or more, and up to 27.2MPa, elongation at break resists after water resistance test up to 233% tensile strength
Tensile strength is dropped by less than 10%, and flammability test has excellent mechanical performance, water resistance, heat resistance up to V-0 grades
And flame retardant property.Comprehensively better than the comparative example 3 using APP fire retardant.
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 (9)
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 containing substituted or unsubstituted
Unsaturated alkyl or at least one of substituted or unsubstituted unsaturated ring alkyl group, R3 be not present or hydrogen atom or
Meet any group of its chemical environment, R5 is Group VIA element or is not present, and X is appointing in oxygen atom, sulphur atom or nitrogen-atoms
It anticipates one kind, n is 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 R1 and R4 is separately substituted or unsubstituted
Alkyl, substituted or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substitution
Or it unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl, substitution or does not take
The miscellaneous alkyl aryl in generation, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted virtue
Oxygroup, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroaryl alkane
Oxygroup, substituted or unsubstituted alkyl heteroaryloxy, substituted or unsubstituted alkylamino, substituted or unsubstituted naphthene amino,
Substituted or unsubstituted fragrant amino, substituted or unsubstituted alkyl fragrant amino, replaces substituted or unsubstituted aryl alkane amino
Or unsubstituted heteroarylalkylamino, substituted or unsubstituted alkyl heteroaryl amino, substituted or unsubstituted alkyl thiol, substitution
Or it is unsubstituted aryl thiol, substituted or unsubstituted carboxylate, substituted or unsubstituted carbonate group, substituted or unsubstituted
Sulfonate group or substituted or unsubstituted phosphonate group in any one；
Preferably, R1 or R4 is separately and in Formulas IGroup is identical.
3. fire retardant according to claim 1 or 2, which is characterized in that the R3 is substituted or unsubstituted alkyl, substitution
Or unsubstituted naphthenic base, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted virtue
Base alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl alkyl or substituted or unsubstituted alkyl are miscellaneous
Any one in aryl.
4. fire retardant according to claim 1-3, which is characterized in that the R6 and R7 is separately hydrogen original
Sub or substituted or unsubstituted alkyl, substituted or unsubstituted naphthenic base, substituted or unsubstituted aryl, replace or do not take
The heteroaryl in generation, substituted or unsubstituted aryl alkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted heteroaryl
Any one in alkyl or substituted or unsubstituted miscellaneous alkyl aryl.
5. fire retardant according to claim 1-4, which is characterized in that the R' and R " are separately substitution
Or it unsubstituted linear chain or branched chain alkylidene, substituted or unsubstituted cycloalkylidene, substituted or unsubstituted arlydene, takes
Generation or unsubstituted inferior heteroaryl, substituted or unsubstituted arylidene alkylene, substituted or unsubstituted alkylidene are sub-
It is any one in aryl, substituted or unsubstituted alkylidene inferior heteroaryl or substituted or unsubstituted inferior heteroaryl alkylidene
Kind.
6. a kind of preparation method of the described in any item reactive flame retardants of claim 1-5, 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 containing substituted or
It is fire-retardant that the organic compound reaction of unsubstituted unsaturated alkyl or substituted or unsubstituted unsaturated ring alkyl obtains reactivity
Agent；
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.
7. a kind of application of the described in any item reactive flame retardants of claim 1-5, which is characterized in that the ring reactivity resistance
Combustion agent is used to prepare moulding material and composite material.
8. a kind of application of the described in any item reactive flame retardants of claim 1-5, which is characterized in that the ring reactivity resistance
Combustion agent is used to prepare unsaturated resin composition.
9. a kind of application of the described in any item reactive flame retardants of claim 1-5, which is characterized in that the reactivity is fire-retardant
Agent is used to prepare glass reinforced plastic.
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| CN112442078B (en) * | 2019-08-28 | 2023-08-29 | 广东广山新材料股份有限公司 | Phosphorus-containing flame retardant with carbon-carbon unsaturated bond, and preparation method and application thereof |
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