CN107629607A - A kind of fireproof coating - Google Patents
A kind of fireproof coating Download PDFInfo
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- CN107629607A CN107629607A CN201610523613.2A CN201610523613A CN107629607A CN 107629607 A CN107629607 A CN 107629607A CN 201610523613 A CN201610523613 A CN 201610523613A CN 107629607 A CN107629607 A CN 107629607A
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Abstract
The invention provides a kind of fireproof coating.The fireproof coating is included as halogen-free flameproof thing shown in the Formulas I of raw material components, and the addition of the flame retardant causes fireproof coating to have good fire protecting performance, while has excellent adhesion strength.The fireproof coating is prepared by the raw material of the component comprising following mass parts：20~40 parts of silicone acrylic emulsions, 16~25 parts of PUA emulsions, 10~25 parts of epoxy resin latexes, 5~25 parts of flame retardants, the addition of the flame retardant cause fireproof coating to have good fire protecting performance.The adhesion strength for the fireproof coating that the present invention is prepared is up to 1.7 2.2MPa, and FAA 8,130 3 reaches 49.3 50.2Kw/m2, fire protecting performance is good, and exposes hot, resistance to acids and bases, salt fog resistance with resistance to, therefore is a kind of fireproof coating with excellent combination property.
Description
Technical field
The present invention relates to the technical field of fire retardant matter, more particularly to a kind of fireproof coating.
Background technology
With continuous improvement of the people to the outward appearance and function of building, steel construction by ten intensity height, good toughness, from heavy and light,
Ten modern architecture industry have been answered in antivibration pinking and good impact resistance, the manufacture of mesh _ easy ten and the features such as use extensively.Steel construction master
If metal material, good heat conductivity, therefore there is fire resistance it is poor, perishable the shortcomings that.When temperature is more than 2500C, material
Vary widely, intensity gradually reduces.When temperature is up to 500 0C, steel, which enter mecystasis, can not continue to carry, and cause to build
Caving in for thing is built, so as to cause casualties and economic loss.Therefore, the fire retardant anticorrosion of steel construction is significant.
In order that product reaches required fire resistance or grade, the fireproof coating currently used for construction steel structure body leads to
Often use such as metal hydroxide combustion inhibitor of aluminium hydroxide hydrate, magnesium hydroxide hydrate containing the crystallization water, Huo Zheju
Ammonium phosphate (APP), the fire retardant of phosphoric acid ester.Chinese patent CN 102876192A disclose a kind of fireproof coating, and it uses poly-
Ammonium phosphate, Firebrake ZB, aluminium hydroxide are less than 100min as fire retardant, the fire endurance of the fireproof coating, and fire protecting performance is inadequate
It is preferable.
The content of the invention
In view of this, one aspect of the present invention provides a kind of fire protecting performance excellent fireproof coating.
A kind of fireproof coating, the halogen-free flameproof thing of raw material components；The halogen-free flameproof thing its there is molecule as shown in formula I
Structure：
In formula I, R1And R2It independently is any inertia nucleophilic group for meeting its chemical environment, R3And R4To meet its change
Learn any organic group of environment, X1And X2It independently is-O-Ar-O- ,-S-R5-S-、-NH-R6-NH-、-NH-R7-O-、-S-R11NH-、-O-R12 -COO- or-S-R13 -Any one in COO-, R5、R6、R7、R8、R9、R10、R11、
R12And R13To meet any organic group of its chemical environment, Y1And Y2It independently is any nucleophilic group for meeting its chemical environment
Group；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In any one or at least two
Combination, m, n are the integer more than or equal to zero；A, b, c, d are the integer more than or equal to zero, and a+b+c+d+2 is equal to phosphorus on M groups
2 times of atom number.In the present invention, it is described to meet that its chemical environment is to refer to atom adjacent thereto to be connected, obtain steady
Fixed is connected chemically key.
Preferably, R1And R2It independently is substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution
Or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, substitution or not
Substituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbon
Any one in perester radical, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group；The alkoxy,
Cycloalkyloxy, aryloxy group, alkoxy aryl, heteroarylalkoxy, alkyl sulfenyl, artyl sulfo, carbonate group, sulfonate group or
The substituent of phosphonate group independently is straight or branched alkyl, alkoxy, cycloalkyloxy, aryl, aryloxy group, arylalkoxy
Any one in base, heteroaryl, alkyl sulfenyl, artyl sulfo, carboxylic acid ester groups, carbonate group, sulfonate group or phosphonate group
Or at least two combination, the substituent do not contain reactive end-capping group；For example, the substituent for do not contain OH ,-
CN、-NH2、-SH、-COOH、-CHO、-CONH2Isoreactivity group；Illustrated with instantiation, when substituent is carboxylic acid ester groups,
It can not be the formic acid ester group that one end still carries carboxyl.
Specifically, R1And R2CH can independently be3O-、CH3CH2O-、CH3S-、CH3CH2CH2S-、CH3COO- or PhO- (Ph
Represent phenyl) in any one.
R in the present invention1And R2Can be that identical group can also be different groups.
Preferably, R3And R4It independently is substituted or unsubstituted straight or branched alkylidene, substituted or unsubstituted Asia
Cycloalkyl, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted arlydene
Alkylidene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene inferior heteroaryl or it is substituted or
Any one in unsubstituted inferior heteroaryl alkylidene.
Specifically, R3And R4- CH can independently be2-、-CH2CH2CH2-、 In any one.
Preferably, R5、R6、R7、R8、R11、R12And R13It independently is substituted or unsubstituted straight or branched alkylidene, takes
Generation or unsubstituted cycloalkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substitution
Or unsubstituted arylidene alkylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene are sub-
Any one in heteroaryl or substituted or unsubstituted inferior heteroaryl alkylidene.
Specifically, R5、R6、R7、R8、R11、R12And R13- CH can independently be2-、-CH2CH2CH2-、 In any one.
Preferably, R9And R10It independently is substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted ring
Alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, take
Generation or unsubstituted heteroaryl, substituted or unsubstituted substituted or unsubstituted aryloxy group, substituted or unsubstituted aryl
Alkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alcoxyl
Base heteroaryl, substituted or unsubstituted heteroaryl oxyalkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkane
Base aryl, substituted or unsubstituted aryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkyl sulfide
Base, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substitution
Or any one in unsubstituted sulfonate group or substituted or unsubstituted phosphonate group.
Specifically, R9And R10- CH can independently be3、-OCH3、-CN、-COOH、-CHO、-CONH2It is or any one in Ph-
Kind.
Preferably, Y1And Y2It independently is substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution
Or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, substitution or not
Substituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbon
Any one in perester radical, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group.
Specifically, Y1And Y2- OCH can independently be3、PhO-、CH3S-, PhS- or CH3Any one in COO-.
In the present invention, substituted or unsubstituted straight chained alkyl or branched alkyl be preferably substituted or unsubstituted C1~
C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) straight chained alkyls or branched alkyl, further preferred C1~
C8 straight chained alkyls or branched alkyl, it is methyl when carbon number is 1, when carbon number is 2, as ethyl.
Substituted or unsubstituted cycloalkyl be preferably substituted or unsubstituted C3~C12 (such as C4, C5, C6, C7, C8,
C9, C10 or C11) cycloalkyl.
Substituted or unsubstituted alkoxy be preferably substituted or unsubstituted C1~C12 (such as C2, C3, C4, C5, C6,
C7, C8, C9, C10 or C11) alkoxy.
Substituted or unsubstituted cycloalkyloxy be preferably substituted or unsubstituted C3~C12 (such as C4, C5, C6, C7,
C8, C9, C10 or C11) cycloalkyloxy.
Substituted or unsubstituted aryl be preferably phenyl, benzyl, naphthyl, Deng.
Substituted or unsubstituted heteroaryl is five yuan or six membered heteroaryl, more preferably substituted or unsubstituted furan
Mutter base or pyridine radicals.
Substituted or unsubstituted aryl alkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) aryl alkyl.
Substituted or unsubstituted alkylaryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylaryl.
Substituted or unsubstituted alkoxy aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkoxy aromatic
Base.
Substituted or unsubstituted heteroaryl alkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl alkane
Base.
Substituted or unsubstituted miscellaneous alkyl aryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkyl heteroaryl
Base.
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 C6-C13 (such as C7, C8, C9, C10, C11 or C12) arlydene.
Substituted or unsubstituted inferior heteroaryl is preferably C5-C13 (such as C6, C7, C8, C9, C10, C11 or C12)
Inferior heteroaryl.
Substituted or unsubstituted alkylenearylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylene
Base arlydene.
Substituted or unsubstituted arylidene alkylene is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkylene
Base arlydene.
Substituted or unsubstituted alkylidene inferior heteroaryl is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12)
Alkylidene inferior heteroaryl.
Substituted or unsubstituted inferior heteroaryl alkylidene is preferably C6-C13 (such as C7, C8, C9, C10, C11 or C12)
Inferior heteroaryl alkylidene.
Substituted or unsubstituted alkoxy heteroaryl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) alkoxy
Heteroaryl.
Substituted or unsubstituted heteroarylalkoxy is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl
Alkoxy.
Substituted or unsubstituted heteroaryl oxyalkyl is preferably C7-C13 (such as C8, C9, C10, C11 or C12) heteroaryl
Oxyalkyl.
Substituted or unsubstituted alkoxy aryl is C7-C12 (such as C8, C9, C10 or C11) aralkoxy.
Substituted or unsubstituted alkyl-aryloxy is preferably C7-C12 (such as C8, C9, C10 or C11) alkyl-aryloxy.
Substituted or unsubstituted alkyl sulfenyl is preferably C1-C8 (such as C1, C2, C3, C4, C5, C6, C7 or C8) alkyl sulfide
Base.
Substituted or unsubstituted artyl sulfo is preferably C7-C12 (such as C8, C9, C10 or C11) artyl sulfo.
Term " substituted " used in the present invention refer to any one or more hydrogen atoms on specified atom by selected from
The substituent substitution of designated groups, condition is that the specified atom is no more than normal valency, and the result substituted is to produce stabilization
Compound.When substituent is oxo group or ketone group (i.e.=O), then 2 hydrogen atoms on atom are substituted.Ketone substitutes
Base is not present on aromatic rings." stable compound " be refer to it is sufficiently strong strongly from reactant mixture separation to effective
Purity is simultaneously configured to compounds effective.
In the present invention, M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2, non-annularity polyphosphazene base M3In one kind or
At least two combination.
Preferably, M includes at least 50wt%M1, at most 30wt%M2And at most 45wt%M3。
In the present invention, M1Content is at least 50wt%, i.e. M1Content can be 50wt~100wt%, M1For main body into
Point.Work as M1When content is 100wt%, then M is not contained2And M3.The typical but non-limiting M of the present invention1Content can be
50wt%, 51wt%, 55wt%, 58wt%, 60wt%, 65wt%, 70wt%, 74wt%, 75wt%, 80wt%, 85wt%,
90wt%, 92wt%, 95wt%, 98wt% or 100wt%.
In the present invention, M2Content is at most 30wt%, that is, is referred to, M2Content can be 0~30wt%.Work as M2Content is
During 0wt%, that is, refer to, do not contain M2.The typical but non-limiting M of the present invention2Content can be 0wt%, 2wt%, 5wt%,
8wt%, 11wt%, 14wt%, 16wt%, 17wt%, 19wt%, 20wt%, 22wt%, 25wt%, 27wt%, 28wt% or
29wt%.
In the present invention, M3Content is at most 45wt%, that is, is referred to, M3Content can be 0~45wt%.Work as M3Content is
During 0wt%, that is, refer to, do not contain M3.The typical but non-limiting M of the present invention3Content can be 0wt%, 2wt%, 5wt%,
8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 23wt%, 25wt%, 27wt%, 28wt%,
30wt%, 32wt%, 35wt%, 38wt%, 40wt%, 43wt% or 45wt%.
In the present invention, M1、M2And M3Mass percent sum is 100%.
In the structural formula I of the present invention, m, n are the integer more than or equal to zero, and m, n can be zero simultaneously, can also be different
When be zero, such as m can be but be not limited to 0,1,2,3,4,5,6,7,8,9 or 10, n can be but be not limited to 0,1,2,3,4,5,
6th, 7,8,9 or 10.
A, b, c, d are the integer more than or equal to zero, and both c, d can not be zero simultaneously, that is, ensure that M institutes band group at least contains
There is a group (such as-SH or-OH) with reactivity.
In the structural formula of the present invention, the group being connected with M is connected with the phosphorus atoms in M.And in formula I
Middle a+b+c+d+2 is equal to 2 times of number of phosphorus atoms on M groups, that is, ensures that phosphorus atoms reach the saturation shape that chemical valence is pentavalent on M
State.
Preferably, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3.
Pay attention to, M1、M2In the expression of structural formula, there is symbolOnly to one kind of " ring-type " structure
Signal.
It is equal in the substituent of all groups or group in its chemical formula the present invention is to provide a kind of halogen-free flameproof thing
Halogen is not contained.
Preferably, halogen-free flameproof thing of the present invention is a kind of in the compound with following structure or at least two groups
Close：
Wherein M is the phosphonitrile base of ring three.
On the other hand, the present invention provides a kind of preparation method of the halogen-free flameproof thing.
The halogen-free flameproof thing of the formula I of the present invention is that nucleophilic substitution occurs with nucleopilic reagent by phosphonitrile chloride to be prepared into
Arrive.
Phosphonitrile chloride refers to M-Cla+b+c+d+2, and nucleopilic reagent refers to R1、R2、-S-R3-SH、-O-R4-OH、X1、X2、Y1
And Y2Corresponding affinity reagent, for example, working as R1For methoxyl group when, it is possible to achieve nucleophilic displacement of fluorine occurs by first with phosphonitrile chloride
The affinity reagent that epoxide is connected on M phosphorus atoms can be methanol or sodium methoxide；Work as R2For methylsulfany (CH3, can be with when S-)
Realize that the affinity reagent that methylsulfany is connected on M phosphorus atoms with phosphonitrile chloride generation nucleophilic substitution can be first
Mercaptan or sodium methyl mercaptide；As-S-R3- SH is-S-CH2CH2During-SH, it is possible to achieve nucleophilic substitution occurs with phosphonitrile chloride
By-S-CH2CH2The affinity reagent that-SH is connected on M phosphorus atoms can be HS-CH2CH2-SH；As-O-R4- OH isWhen, it is possible to achieve nucleophilic substitution occurs with phosphonitrile chloride willIt is connected to M phosphorus
Affinity reagent on atom can beSame method can realize X1、X2、Y1And Y2Connection, X1And X2
Corresponding nucleopilic reagent be at least with M nucleophilic substitution can occur containing two and by X1And X2It is connected on M phosphorus atoms
The nucleopilic reagent of active reactive group.
At least containing a group-SH or-OH with reactivity in the halogen-free flameproof thing of formula I.C, which person is in d
Zero, then show that the reactant for participating in necleophilic reaction does not contain the reactant corresponding to it.
In the nucleophilic substitution, the chlorine in phosphonitrile chloride is substituted.Necleophilic reaction can use known in this field
Method complete, such as refer to " progress of polyphosphazene, Zhang Hongwei etc., material Leader 2010 year the 7th phase of volume 24 ".
The instantiation of the catalyst used in necleophilic reaction has the metal chlorides such as zinc chloride, magnesium chloride, aluminium chloride or borontrifluoride
The lewis base such as boron and its complex compound or sodium hydroxide.These catalyst can one or more be used in mixed way, the present invention in
Have no special regulation.Here " phosphonitrile chloride " refers to the compound that M groups are connected with Cl in formula (I).As for phosphonitrile
Chloride can use known solvent, catalyst to be synthesized in known reaction scheme, can also use phosphorus pentachloride and chlorination
Ammonium is synthesized after phosphonitrilic chloride compound according to known methods, handles purification by physical method or does not purify direct system
Make, its PCl5+NH4Cl→1/n(NPCl2) n+4HCl, it is mainly tripolymer (PNCl in the reaction product2)3(that is, chlordene ring
Three phosphonitriles) and the tetramer (PNCl2)4, reaction product is again by by the way that slowly distillation can obtain pure chlordene ring in 60 DEG C of vacuum
Three phosphonitriles.The phosphonitrile of chloro ring more than four and chloro non-annularity polyphosphazene can also be prepared by prior art.
In above-mentioned preparation method, nucleopilic reagent necessarily includes the nucleopilic reagent containing at least two active reactive groups
(i.e.-S-R3-SH、-O-R4-OH、X1、X2Corresponding affinity reagent, R3、R4、X1、X2Restriction is same as above), to obtain tying shown in formula (I)
The attachment structure of group and ensure in structure shown in formula I at least to block containing a reactivity in the halogen-free flameproof compound of structure
Group.The example of the nucleopilic reagent of at least two active reactive groups can include but is not limited to hydroquinones, resorcinol, naphthalene
Diphenol, mixing benzenediol, 1,4- naphthols, bisphenol-A, bisphenol S, Bisphenol F, the mercaptan of 1,4- phenyl two, 1,2- dithioglycols, 1,3- third
Two mercaptan, terephthalic acid (TPA) etc..
Except it is above-mentioned containing the nucleopilic reagent of at least two active reactive groups in addition to, can also use contain an active reaction base
Other nucleopilic reagents of group, if monohydric alcohol (for example, methanol, ethanol) or its sodium salt, phenol, unary carboxylation are (for example, acetic acid
Sodium), monoamine (for example, methylamine, ethamine), unitary mercaptan (for example, methyl mercaptan, ethyl mercaptan) etc..
In the reaction of nucleopilic reagent and phosphonitrile chloride, the nucleophilic examination containing an active reactive group can be first used
Agent and phosphonitrile chloride react, and part substitutes the chlorine in phosphonitrile chloride, then use again and described contain at least two active reactions
The nucleopilic reagent of group reacts with phosphonitrile chloride, to obtain formula (I) structure halogen-free flameproof thing.
The raw material of the fireproof coating of the present invention includes the component of following mass parts：20~40 parts of silicone acrylic emulsions, 16~25 parts
PUA emulsions, 10~25 parts of epoxy resin latexes, 5~25 parts of flame retardants.
Silicone acrylic emulsion is organosilicon-modified acrylic emulsion, and it prepares the known method that can use this area, that is, using has
Machine silicon monomer (KH570), acrylic monomers (MMA etc.) are obtained by initiator (persulfate) is by emulsion polymerization.
PUA emulsions are acrylic acid modified polyurethane emulsion, and it prepares the known method that can use this area, i.e., using polynary
Alcohol monomer (PPG), polyisocyanates (IPDI) and acrylate monomers (HEMA) are logical in catalyst (such as pink salt)
Emulsion polymerization is crossed to obtain.
Certain three of the above raw emulsion silicone acrylic emulsion, PUA emulsions, epoxy resin latex can be according to the need of actual product
Ask pick up from it is commercially available.
In the fireproof coating of the present invention, the dosage of typical but non-limiting silicone acrylic emulsion is 21 parts, 22 parts, 24 parts,
26 parts, 28 parts, 30 parts, 33 parts, 35 parts, 37 parts or 39 parts.
In the fireproof coating of the present invention, the dosages of typical but non-limiting PUA emulsions is 17 parts, 18 parts, 19 parts, 20
Part, 21 parts, 22 parts, 23 parts or 24 parts.
In the fireproof coating of the present invention, the dosage of typical but non-limiting epoxy resin latex is 11 parts, 12 parts, 14
Part, 16 parts, 18 parts, 20 parts, 21 parts, 22 parts, 23 parts or 24 parts.
In the fireproof coating of the present invention, the dosage of typical but non-limiting halogen-free flameproof thing of the present invention is 6
Part, 8 parts, 10 parts, 13 parts, 15 parts, 18 parts, 20 parts, 21 parts, 22 parts, 23 part, parts or 24 parts.
According to being actually needed, on the basis of above-mentioned raw materials, the raw material of the fireproof coating can also include following mass parts
Component：3~7 parts of (such as 4 parts, 4.5 parts, 5 parts, 5.5 parts or 6 parts) auxiliary agents, 2~5 parts (such as 3 parts, 3.5 parts, 4 parts, 4.5
Part or 4.8 parts) surfactant, 5~15 parts (such as 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts or 14 parts) fill out
Material.
Dispersant is preferably dispersant DISPERBYK-163.Thixotropic agent is preferably aerosil.Levelling agent is preferably
Levelling agent Ciba EFKA3777.Defoamer is preferably defoamer FFKA2722.
Surfactant is SDS, SDBS, OP series of surfactants, one kind in NP series of surfactants or at least
Two kinds of combination.SDS is lauryl sodium sulfate, and SDBS is neopelex, and OP series of surfactants specifically has
OP-10, OP-9 etc..
Filler can do conventional selection according to being actually needed, such as can be with titanium dioxide, aluminum oxide, frog stone flour, kaolin, carbon
One kind or at least two combination in sour calcium, silica flour, barium sulfate, cenosphere.
The preparation method of fireproof coating of the present invention can be prepared using coating industry personnel according to the commonsense method of coating, i.e.,
Each raw material is sufficiently mixed the particle diameter of established practice provisioning request by mixing apparatus (cutter etc.).
Above-mentioned term " ××× base or group ", which refers to, sloughs one or more hydrogen atoms in ××× molecular structure of compounds
Or remaining part after other atoms or atomic group.
Relative to prior art, the invention has the advantages that：
The fireproof coating of the anti-flammability of the present invention is included as halogen-free flameproof thing shown in the Formulas I of raw material components, the flame retardant
Addition cause fireproof coating that there is good fire protecting performance, while there is excellent adhesion strength.By including following mass parts
The raw material of component the fireproof coating is prepared：20~40 parts of silicone acrylic emulsions, 16~25 parts of PUA emulsions, 10~25 parts of rings
Oxygen tree fat liquor, 5~25 parts of flame retardants, the addition of the flame retardant cause fireproof coating to have good fire protecting performance.The present invention
The adhesion strength for the fireproof coating being prepared is up to 1.7-2.2MPa, and FAA 8130-3 reach 49.3-50.2Kw/m2, fire prevention
It is functional, and hot, resistance to acids and bases, salt fog resistance are exposed with resistance to, therefore be a kind of there is excellent combination property
Fireproof coating.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
In the examples below, raw materials used phosphonitrile chloride (such as hexachlorocyclotriph,sphazene) can be according to conjunction of the present invention
Synthesize to obtain into method or synthetic method known in the art, remaining raw material can be by being commercially available.
Embodiment 1
In the present embodiment, halogen-free flameproof thing has following structure：
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, double is put into three mouthfuls of 2000ml glass reactors with agitating device
Phenol A 3mol, sodium methyl mercaptide 3mol, stir, while leading to nitrogen, be warming up to 60 DEG C, 20% sodium hydroxide is instilled with 60min
Solution 620g, kept for 60 DEG C of temperature, 15 hours of stirring reaction.After reaction, with the moisture in physical method removal system, after
The insoluble matter in the system of removing is filtered off, solvent in system is distilled, obtains the flame-retardant compound containing above-mentioned substance.
Proton nmr spectra sign is carried out to obtained flame-retardant compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):6.6-7.0 (m, 24H, phenyl ring on hydrogen), 5.0 (s, 3H, phenolic hydroxyl group hydrogen), 2.0 (m,
9H,SCH 3) 1.6 (m, 18H, bisphenol-A group on methyl hydrogen).
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm- of methyl ether1, P-O-C key absworption peaks 1035cm-1, the skeleton of phenyl ring shakes in bisphenol-A group
Dynamic absworption peak 1611cm-1、1509cm-1、1446cm-1, phenolic hydroxyl group absworption peak 3610cm-1、1260cm- 1。
According to mass parts by 5 parts of flame retardants, 20 parts of silicone acrylic emulsions, 25 parts of PUA emulsions, 25 parts of epoxy resin latexes, 1 part point
Powder DISPERBYK-163,1 part of levelling agent Ciba EFKA3777,1 part of defoamer FFKA2722,2 parts of SDS, 5 parts of titanium dioxides,
To stir 30min under 500~1000rpm rotating speeds, then 2h disperseed using high-speed shearing machine, the particle diameter of coating to be determined reaches predetermined
After particle diameter, that is, obtain fireproof coating product.
Embodiment 2
In the present embodiment, halogen-free flameproof thing has following structure：
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, second are put into three mouthfuls of 2000ml glass reactors with agitating device
Two mercaptan 6mol, stir, lead to nitrogen, while being warming up to 60 DEG C, 20% sodium hydroxide solution is instilled with 60min
620g, kept for 60 DEG C of temperature, 15 hours of stirring reaction, after reaction, with the moisture in physical method removal system, after elimination
Except the insoluble matter in system, solvent in system is distilled, obtains the flame-retardant compound containing above-mentioned substance.
Proton nmr spectra sign is carried out to obtained flame-retardant compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ2.8(m,24H,HS-CH 2CH 2S-),1.5(s,6H,HS-CH2CH2S-)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1, CH2- S absworption peak 2980cm-1,-SH
Absworption peak 2560cm-1。
According to mass parts by 25 parts of flame retardants, 40 parts of silicone acrylic emulsions, 25 parts of PUA emulsions, 10 parts of epoxy resin latexes, 2 parts
Dispersant DISPERBYK-163,3 parts of levelling agent Ciba EFKA3777,2 parts of defoamer FFKA2722,5 parts of SDS, 15 parts of titanium whites
Powder, to stir 30min under 500~1000rpm rotating speeds, then 2h disperseed using high-speed shearing machine, the particle diameter of coating to be determined reaches
After predetermined particle diameter, that is, obtain fireproof coating product.
Embodiment 3
In the present embodiment, halogen-free flameproof thing has following structure：
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, benzene are put into three mouthfuls of 2000ml glass reactors with agitating device
Thiophenol 3mol, sodium methoxide 2mol, ethylene glycol 1mol, stir, while leading to nitrogen, be warming up to 60 DEG C, 20% is instilled with 60min
Sodium hydroxide solution 620g, 60 DEG C of temperature are kept, 15 hours of stirring reaction, then add hexachlorocyclotriph,sphazene 1mol, are continued
Reaction 2 hours, hydroquinones 2mol, sodium methoxide 3mol are added afterwards, continue reaction 6 hours.After reaction, removed with physical method
Moisture in system, the insoluble matter in removal system is refiltered, distill solvent in system, obtain the resistance containing above-mentioned substance
Retardant compound.
Proton nmr spectra sign is carried out to obtained flame-retardant compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ7.0-7.2(m,15H,Hydrogen on phenyl ring in group), 6.6 (m,
8H,Hydrogen on phenyl ring in group), 5.0 (m, 2H,Hydrogen on hydroxyl in group), 3.7 (d,
4H,O-CH 2CH 2O-),3.4(t,15H,O-CH 3)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1, CH2- O absworption peak 2983cm-1, phenol
Hydroxyl absorption peak 3610cm-1、1260cm-1。
According to mass parts by 15 parts of flame retardants, 30 parts of silicone acrylic emulsions, 20 parts of PUA emulsions, 15 parts of epoxy resin latexes, 2 parts
Dispersant DISPERBYK-163,2 parts of levelling agent Ciba EFKA3777,1 part of defoamer FFKA2722,3 parts of SDS, 10 parts of titanium whites
Powder, to stir 30min under 500~1000rpm rotating speeds, then 2h disperseed using high-speed shearing machine, the particle diameter of coating to be determined reaches
After predetermined particle diameter, that is, obtain fireproof coating product.
Embodiment 4
In the present embodiment, halogen-free flameproof thing has following structure：
Hexachlorocyclotriph,sphazene 1mol, acetone 250ml, second are put into three mouthfuls of 2000ml glass reactors with agitating device
Two mercaptan 5mol and hydroquinones 1mol, stir, while leading to nitrogen, be warming up to 60 DEG C, 20% hydrogen-oxygen is instilled with 60min
Change sodium solution 620g, keep 60 DEG C of temperature, 15 hours of stirring reaction, then add hexachlorocyclotriph,sphazene 1mol, continue reaction 5
Hour, bisphenol-A 1mol, sodium methoxide 4mol are added afterwards, continue reaction 10 hours.After reaction, with physical method removal system
Moisture, refilter the insoluble matter in removal system, distill solvent in system, obtain the fire-retardant chemical combination containing above-mentioned substance
Thing.
Proton nmr spectra sign is carried out to obtained flame-retardant compound, it is as a result as follows：
1H NMR(CDCl3,500MHz):δ 6.5-7.0 (m, 12H, phenyl ring on hydrogen), 5.0 (s, 1H, phenolic hydroxyl group hydrogen), 3.4
(t,12H,O-CH 3), 2.8 (m, 20H, HS-CH 2CH 2S-), 1.7 (s, 30H, bisphenol-A on methyl hydrogen), 1.5 (s, 5H,HS-
CH2CH2S-)。
The position of infrared spectrum characteristic peak：The characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P- in phosphazene backbone
N 874cm-1, the absworption peak 2995cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1, CH2- O absworption peak 2983cm-1, it is double
The skeletal vibration absworption peak 1611cm of phenyl ring in phenol A groups-1、1509cm-1、1446cm-1, phenolic hydroxyl group absworption peak 3610cm-1、
1260cm-1。
According to mass parts by 15 parts of flame retardants, 40 parts of silicone acrylic emulsions, 25 parts of PUA emulsions, 15 parts of epoxy resin latexes, 2 parts
Dispersant DISPERBYK-163,1 part of levelling agent Ciba EFKA3777,2 parts of defoamer FFKA2722,3 parts of SDS, 10 parts of titanium whites
Powder, to stir 30min under 500~1000rpm rotating speeds, then 2h disperseed using high-speed shearing machine, the particle diameter of coating to be determined reaches
After predetermined particle diameter, that is, obtain fireproof coating product.
Comparative example 1
In this example, CABLE MATERIALS include using commercially available APP as flame retardant, according to mass parts by 15 parts of flame retardants,
40 parts of silicone acrylic emulsions, 25 parts of PUA emulsions, 15 parts of epoxy resin latexes, 2 parts of dispersant DISPERBYK-163,1 part of levelling agent
Ciba EFKA3777,2 parts of defoamer FFKA2722,3 parts of SDS, 10 parts of titanium dioxides, to be stirred under 500~1000rpm rotating speeds
30min, then 2h is disperseed using high-speed shearing machine, after the particle diameter of coating to be determined reaches predetermined particle diameter, that is, obtain fire prevention apply
Expect product.
The test as shown in following table -1 is done to the cable products of above-mentioned all embodiments and comparative example, as a result as shown in Table-1
(in view of specific method of testing has been well known to those skilled in the art, method is no longer described in detail at this, such as refer to national standard
GB14907-2002)：
Table -1
The test data of above table, show that highest rate of heat release of the present invention will be much smaller than the 103.4Kw/m of comparative example2,
About comparative example is general, and is no more than 65Kw/m2, illustrating the fireproof coating of the present invention has excellent fire protecting performance.
Applicant states that the present invention illustrates the fireproof coating of the present invention, but not office of the invention by above-described embodiment
It is limited to above-described embodiment, that is, does not mean that the present invention has to rely on above-described embodiment and could implemented.The technology of art
Personnel it will be clearly understood that any improvement in the present invention, the addition of equivalence replacement and auxiliary element to each raw material of product of the present invention,
Selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of fireproof coating, it is characterised in that include the halogen-free flameproof thing as raw material components；Its tool of the halogen-free flameproof thing
Just like the molecular structure shown in formula I：
In formula I, R1And R2It independently is any inertia nucleophilic group for meeting its chemical environment, R3And R4To meet its chemical environment
Any organic group, X1And X2It independently is-O-Ar-O- ,-S-R5-S-、-NH-R6-NH-、-NH-R7-O-、-S-R11NH-、-O-R12COO- or-S-R13Any one in COO-, R5、R6、R7、R8、R9、R10、R11、R12
And R13To meet any organic group of its chemical environment, Y1And Y2It independently is any nucleophilic group for meeting its chemical environment
Group；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In any one or at least two
Combination, m, n are the integer more than or equal to zero；A, b, c, d are that both integers, c, d more than or equal to zero can not be zero simultaneously, and a+
B+c+d+2 is equal to 2 times of number of phosphorus atoms on M groups.
2. fireproof coating according to claim 1, it is characterised in that R1And R2It independently is substituted or unsubstituted alcoxyl
Base, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl, substitution
Or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substitution or not
Substituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group or substituted or unsubstituted
Any one in phosphonate group；The alkoxy, cycloalkyloxy, aryloxy group, alkoxy aryl, heteroarylalkoxy, alkyl
Sulfenyl, artyl sulfo, carbonate group, the substituent of sulfonate group or phosphonate group independently are straight or branched alkyl, alcoxyl
Base, cycloalkyloxy, aryl, aryloxy group, alkoxy aryl, heteroaryl, alkyl sulfenyl, artyl sulfo, carboxylic acid ester groups, carbonic ester
In base, sulfonate group or phosphonate group any one or at least two combination, the substituent do not contain reactive end-blocking
Group；
Preferably, R3And R4It independently is substituted or unsubstituted straight or branched alkylidene, substituted or unsubstituted sub- cycloalkanes
Base, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substituted or unsubstituted arlydene alkylene
Base, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene inferior heteroaryl or substituted or do not take
Any one in the inferior heteroaryl alkylidene in generation；
Preferably, R5、R6、R7、R8、R11、R12And R13Independently be substituted or unsubstituted straight or branched alkylidene, substitution
Or unsubstituted cycloalkylidene, substituted or unsubstituted arlydene, substituted or unsubstituted inferior heteroaryl, substitution or not
Substituted arylidene alkylene, substituted or unsubstituted alkylenearylene, substituted or unsubstituted alkylidene Asia heteroaryl
Any one in base or substituted or unsubstituted inferior heteroaryl alkylidene；
Preferably, R9And R10Independently be substituted or unsubstituted straight or branched alkyl, substituted or unsubstituted cycloalkyl,
Substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aryl, substitution or
Unsubstituted heteroaryl, substituted or unsubstituted substituted or unsubstituted aryloxy group, substituted or unsubstituted alkoxy aryl,
Substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted heteroarylalkoxy, substituted or unsubstituted alkoxy heteroaryl
Base, substituted or unsubstituted heteroaryl oxyalkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkyl virtue
Base, substituted or unsubstituted aryl alkyl, substituted or unsubstituted miscellaneous alkyl aryl, substituted or unsubstituted alkyl sulfenyl, take
Generation or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonate group, substitution or do not take
Any one in the sulfonate group in generation or substituted or unsubstituted phosphonate group；
Preferably, Y1And Y2It independently is substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substitution or not
Substituted aryloxy group, substituted or unsubstituted alkoxy aryl, substituted or unsubstituted heteroarylalkoxy, substitution or unsubstituted
Alkyl sulfenyl, substituted or unsubstituted artyl sulfo, substituted or unsubstituted carboxylic acid ester groups, substituted or unsubstituted carbonic ester
Any one in base, substituted or unsubstituted sulfonate group or substituted or unsubstituted phosphonate group；
Preferably, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3.
3. fireproof coating according to claim 1 or 2, it is characterised in that the halogen-free flameproof thing is with following structure
Compound in it is a kind of or at least two combination：
Wherein M is the phosphonitrile base of ring three.
4. according to the fireproof coating any one of claim 1-3, it is characterised in that M includes at least 50wt%M1, at most
30wt%M2And at most 45wt%M3。
5. according to the fireproof coating any one of claim 1-4, it is characterised in that the raw material of the fireproof coating includes
The component of following mass parts：20~40 parts of silicone acrylic emulsions, 16~25 parts of PUA emulsions, 10~25 parts of epoxy resin latexes, 5~25
Halogen-free flameproof thing any one of part 1-4.
6. fireproof coating according to claim 5, it is characterised in that the raw material of the fireproof coating also includes following quality
The component of part：3~7 parts of auxiliary agents, 2~5 parts of surfactants, 5~15 parts of fillers.
7. fireproof coating according to claim 6, it is characterised in that the auxiliary agent be dispersant, levelling agent, defoamer,
One kind or at least two combination in thixotropic agent.
8. fireproof coating according to claim 7, it is characterised in that the dispersant is dispersant DISPERBYK-163；
Preferably, the thixotropic agent is aerosil；
Preferably, the levelling agent is levelling agent Ciba EFKA3777；
Preferably, the defoamer is defoamer FFKA2722.
9. fireproof coating according to claim 6, it is characterised in that the surfactant is SDS, SDBS, OP series
Surfactant, one kind in NP series of surfactants or at least two combination.
10. fireproof coating according to claim 6, it is characterised in that the filler is titanium dioxide, aluminum oxide, frog stone
One kind or at least two combination in powder, kaolin, calcium carbonate, silica flour, barium sulfate, cenosphere.
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