CN104893539B - Preparation method of hydrophobic and flame-retardant PU (polyurethane) coating - Google Patents
Preparation method of hydrophobic and flame-retardant PU (polyurethane) coating Download PDFInfo
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Abstract
The invention discloses a preparation method of a hydrophobic and flame-retardant PU (polyurethane) coating. The method comprises steps as follows: I, weighing out various raw materials; II, evenly mixing the raw materials to obtain a mixture; III, dropwise adding polyisocyanate and a catalyst for a reaction, and then adding organic silicon for a continuous reaction to obtain a prepolymer; IV, dropwise adding water for emulsification, and performing vacuum pumping to remove a solvent so as to obtain the hydrophobic and flame-retardant PU coating. According to the method, the utilization efficiency of natural renewable resources, namely, cyclodextrin and rosin, can be improved, a rigid cyclic structure is introduced into PU, defects that existing water-based PU coatings are poorer in water resistance, heat resistance and surface property are overcome, a flame-retardant chain segment is introduced into a PU skeleton structure, the intrinsic flame-retardant PU coating is synthesized, the defect that additive flame-retardant PU is poor in mechanical property is overcome, besides, the organic silicon is used for modification, the defect that the water-based PU coatings are poor in water resistance is further overcome, the PU coating capable of being stored stably can be obtained, and comprehensive properties of the PU coating are improved.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of preparation side of hydrophobic flame-retardant polyurethane coating
Method.
Background technology
Polyurethane is widely used in the fields such as paper-making industry, building coating, adhesive, ink and leather.Use at present
It is combustible material that polyurethane material is most of, and in today that fire takes place frequently, developing Flame retardant polyurethane material becomes the heat in epoch
Point.Although by way of physics adds fire retardant can give material certain fire resistance, fire retardant and polymer phase
Capacitive is poor, easily migrates or precipitate into material surface, destroys material mechanical performance, therefore, in the knot of synthesis of polyurethane material
Flame-retardant composition is introduced in llex cornuta frame, is given material intrinsic fire resistance, is become the focus of Recent study.
Aqueous polyurethane coating is compared with solvent based coating, has the advantages that environment-protecting asepsis pollution is little, but due to aqueouss
Hydrophilic group is introduced on the strand of polyurethane coating, the water for being absorbed is worked with the polar group in polyurethane, formed
Hydrogen bond, reduces the effect of the hydrogen bond between polyurethane molecular, reduces the mechanical strength of coating so that polyurethane coating exists
There is significant limitation in practical application.Therefore, while improving the fire resistance and surface property of polyurethane material, improve which
Resistance to water, the aqueous polyurethane coating for obtaining high comprehensive performance become everybody common target.
The content of the invention
The technical problem to be solved is for above-mentioned deficiency of the prior art, there is provided a kind of hydrophobic fire-retardant
The preparation method of type polyurethane coating, the method can improve the utilization ratio of natural reproducible resource cyclodextrin and Colophonium, will
Rigid annular structure is introduced in polyurethane, overcome existing aqueous polyurethane coating resistance to water, thermostability and surface property compared with
Poor shortcoming, by fire-retardant segment is introduced in polyurethane skeleton structure, synthesizes Intrinsical flame retardant polyurethane coating, overcomes addition
The shortcoming of type flame retardant polyurethane bad mechanical property, and using organic-silicon-modified, further overcome aqueous polyurethane coating water-fast
Property difference shortcoming, obtain the polyurethane coating that stably can be deposited, improve the combination property of polyurethane coating.
To solve above-mentioned technical problem, the technical solution used in the present invention is：A kind of hydrophobic flame-retardant polyurethane coating
Preparation method, it is characterised in that comprise the following steps：
Step one, the various raw materials for weighing following weight portion：20～90 parts of glycol composition, 5～40 parts of fire retardant are molten
20～60 parts of agent, 5～30 parts of hydrophilic chain extender, 5～50 parts of nertralizer, 0.05～3 part of catalyst, 5～30 parts of organosilicon；It is described
Glycol composition is mixed by biomass-based polyhydric alcohol and polymer polyatomic alcohol, biomass-based in the glycol composition
The mass content of polyhydric alcohol is 10%～25%, balance of polymer polyatomic alcohol；The biomass-based polyhydric alcohol is modified rosin
Or hydroxyalkylated cyclodextrins, the polymer polyatomic alcohol is PEPA or polyether polyol, and the solvent is acetone；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 30
DEG C～60 DEG C under the conditions of mix homogeneously, obtain mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 50 DEG C～90 DEG C, question response are carried out after 4h～10h to reaction system
Organosilicon described in middle addition step one, stops after continuing reaction 1h～3h, obtains performed polymer；It is different in the polyisocyanates
Described in cyanic acid ester group and step one, in glycol composition, the mol ratio of hydroxyl is (1.1～3):1；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C～5 DEG C, the Deca water in the performed polymer,
Emulsifying is carried out to the performed polymer under stirring condition, then evacuation removes the solvent, obtain hydrophobic flame-retardant polyurethane and apply
Material；The quality consumption of the water be make the hydrophobic flame-retardant polyurethane coating solid content be 20wt%～55wt%.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterised in that weighed in step one
Various raw materials are respectively：30～80 parts of glycol composition, 10～30 parts of fire retardant, 30～50 parts of solvent, hydrophilic chain extender 5～
20 parts, 10～40 parts of nertralizer, 1～3 part of catalyst, 5～25 parts of organosilicon.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterised in that the various raw materials for being weighed
Respectively：80 parts of polyhydric alcohol, 20 parts of fire retardant, 40 parts of solvent, 5 parts of hydrophilic chain extender, 10 parts of nertralizer, 3 parts of catalyst are organic
5 parts of silicon.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterised in that hydrophilic described in step one
Chain extender be dihydromethyl propionic acid, dihydroxy half ester and diaminobenzoic acid in one or more；The nertralizer is
Pentamethyl-diethylenetriamine, N, one or more in N- dimethyl cyclohexyl amines, triethylene diamine and triethylamine.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterised in that hydrophilic described in step one
Chain extender is N methyldiethanol amine, and the nertralizer is acetic acid.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterised in that be modified described in step one
Colophonium is Jing maleic acids and glycol modified Colophonium, and the hydroxyalkylated cyclodextrins are that hydroxypropyl cyclodextrin or ethoxy ring are pasted
Essence；The fire retardant is (double (2- ethoxys) the aminomethy-lenephosphonic acids diethylesters of N, N-), the oxidation of double (4- hydroxy phenyls) phenyl
One or more in phosphine, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterised in that polyester described in step one
Polyhydric alcohol is polycaprolactone, polybutylene terephthalate (PBT), polyethylene terephthalate and polyadipate -1,4- fourths two
One or more in alcohol ester；The polyether polyol is Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol, PolyTHF
One or more in ether and poly(ethylene oxide).
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterised in that polyisocyanate described in step 3
Cyanate is toluene di-isocyanate(TDI), isophorone diisocyanate, methyl diphenylene diisocyanate, two isocyanide of hexa-methylene
One or more in acid esters and hexamethylene diisocyanate trimer.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterised in that be catalyzed described in step 3
Agent be dibutyl tin laurate, stannous octoate and three n-butylbenzoic acid stannum in one or more.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterised in that organic described in step 3
Silicon be KH-550, KH-560 and KH-570 in one or more.
The present invention has advantages below compared with prior art：
1st, in the present invention, modified rosin and hydroxyalkylated cyclodextrins are to ensure biomass (Colophonium or cyclodextrin) knot substantially
On the premise of structure (rigid annular structure), a certain degree of modified, imparting biological surface is carried out to the molecular structure of biomass
New functional group, can greatly increase the water solublity of biomass, improve reactivity worth, meanwhile, modified rosin or hydroxyalkylation ring
The rigid backbone of dextrin is introduced in polyurethane structural, it is possible to increase the resistance to water of polyurethane, glossiness and solvent corrosion corrosion.
2nd, the present invention can improve the utilization ratio of natural reproducible resource cyclodextrin and Colophonium, and rigid annular structure is drawn
Enter in polyurethane, the shortcoming for overcoming existing aqueous polyurethane coating resistance to water, thermostability and surface property poor, by poly-
Fire-retardant segment is introduced in urethane framing structure, is synthesized Intrinsical flame retardant polyurethane coating, is overcome additive flame flame-retardant polyurethane machine
The shortcoming of tool poor performance, and using organic-silicon-modified, further overcome the shortcoming of aqueous polyurethane coating poor water resistance, obtain
The polyurethane coating that stably can be deposited, improves the combination property of polyurethane coating.
3rd, fire retardant used in the present invention is while fire retardation is played, additionally it is possible in polyurethane molecular chain structure
Serve as chain extender, be advantageously implemented the intrinsic fire-retardant of polyurethane, while do not weaken its mechanical performance, hydrophobic resistance prepared by the present invention
28 and above (ASTM D2863 standard testing results), (UL94 is marked the limited oxygen index of combustion type polyurethane to reach Vo ranks
Quasi- measurement result), with good flame retardant effect.
Below by drawings and Examples, technical scheme is described in further detail.
Description of the drawings
Fig. 1 is the thermogravimetric curve of hydrophobic flame-retardant polyurethane coating prepared by embodiment 1.
Fig. 2 is the thermogravimetric curve of hydrophobic flame-retardant polyurethane coating prepared by embodiment 3.
Fig. 3 is the thermogravimetric curve of hydrophobic flame-retardant polyurethane coating prepared by embodiment 5.
Fig. 4 is the thermogravimetric curve of hydrophobic flame-retardant polyurethane coating prepared by embodiment 7.
Specific embodiment
Embodiment 1
The present embodiment is comprised the following steps：
Step one, the various raw materials for weighing following weight portion：80 parts of polyhydric alcohol, 20 parts of fire retardant, 40 parts of solvent, hydrophilic expansion
5 parts of chain agent, 10 parts of nertralizer, 3 parts of catalyst, 5 parts of organosilicon；The glycol composition is by biomass-based polyhydric alcohol and polymerization
Thing polyhydric alcohol is mixed, and in the glycol composition, the mass content of biomass-based polyhydric alcohol is 12.5%, balance of poly-
Compound polyhydric alcohol；The biomass-based polyhydric alcohol is hydroxypropyl cyclodextrin, and the polymer polyatomic alcohol is Polyethylene Glycol；It is described molten
Agent is acetone, and the hydrophilic chain extender is dihydromethyl propionic acid, and the fire retardant is (double (2- ethoxys) aminomethylenes of N, N-
Diethyl phosphonate), the nertralizer is pentamethyl-diethylenetriamine；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 60
Mix homogeneously under the conditions of DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 75 DEG C, question response add step one in reaction system after carrying out 4h
Described in organosilicon, continue reaction 1h after stop, obtaining performed polymer；NCO and step one in the polyisocyanates
Described in glycol composition the mol ratio of hydroxyl be 2:1；The polyisocyanates be toluene di-isocyanate(TDI), the catalysis
Agent is dibutyl tin laurate, and the organosilicon is KH-560；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 30wt%.
From figure 1 it appears that hydrophobic flame-retardant polyurethane coating prepared by embodiment 1 is under the conditions of 252 DEG C and 270 DEG C
Weight-loss ratio respectively may be about 5% and 10%, determine the poly- ammonia of the hydrophobic flame retardant type using LFY-606B type digital display oxygen index measurers
The limited oxygen index of ester paint is 28, and according to UL94 standard tests, its fire resistance index can reach Vo ranks, using MCAT
It is 92 ° that type contact angle instrument determines the surface contact angle of the hydrophobic flame-retardant polyurethane coating, and water absorption rate is 2.6%, explanation
The hydrophobic flame-retardant polyurethane coating has good thermostability, anti-flammability and hydrophobicity.
Embodiment 2
The present embodiment is same as Example 1, and its difference is：Polymer polyatomic alcohol described in step one is poly- the third two
Alcohol, polytetramethylene glycol, PTMG or poly(ethylene oxide), or be Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol, poly- tetrahydrochysene
In furan ether and poly(ethylene oxide) at least two；The hydrophilic chain extender is dihydroxy half ester or diaminobenzoic acid, or
For at least two in dihydromethyl propionic acid, dihydroxy half ester and diaminobenzoic acid；The fire retardant is double (4- hydroxy benzeness
Base) phenyl phosphine oxide, tetrabromo-benzene anhydride diol or dibromoneopentyl glycol, or be (double (2- ethoxys) aminomethylene phosphines of N, N-
Diethyl phthalate), in double (4- hydroxy phenyls) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycols at least two；Institute
Nertralizer is stated for N, N- dimethyl cyclohexyl amines, triethylene diamine or triethylamine, or be pentamethyl-diethylenetriamine, N, N- diformazans
In basic ring hexylamine, triethylene diamine and triethylamine at least two；
Polyisocyanates described in step 3 is isophorone diisocyanate, methyl diphenylene diisocyanate, six sub-
Methyl diisocyanate or hexamethylene diisocyanate trimer, or be toluene di-isocyanate(TDI), two isocyanide of isophorone
In acid esters, methyl diphenylene diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer extremely
It is few two kinds；The catalyst is stannous octoate or three n-butylbenzoic acid stannum, or is dibutyl tin laurate, stannous octoate
With at least two in three n-butylbenzoic acid stannum；The organosilicon KH-550 or KH-570, or be KH-550, KH-560 and
In KH-570 at least two.
Hydrophobic flame-retardant polyurethane coating manufactured in the present embodiment has good thermostability, anti-flammability and hydrophobicity.
Embodiment 3
The present embodiment is comprised the following steps：
Step one, the various raw materials for weighing following weight portion：60 parts of polyhydric alcohol, 15 parts of fire retardant, 30 parts of solvent, hydrophilic expansion
9 parts of chain agent, 5 parts of nertralizer, 2 parts of catalyst, 30 parts of organosilicon；The glycol composition is by biomass-based polyhydric alcohol and polymerization
Thing polyhydric alcohol is mixed, and in the glycol composition, the mass content of biomass-based polyhydric alcohol is 16.7%, balance of poly-
Compound polyhydric alcohol；The biomass-based polyhydric alcohol is hydroxyethyl cyclodextrin, and the polymer polyatomic alcohol is Polyethylene Glycol and poly- third
(mass ratio of Polyethylene Glycol and polypropylene glycol is 1 to glycol:1)；The solvent is acetone, and the hydrophilic chain extender is dihydroxymethyl
(mass ratio of dihydromethyl propionic acid and dihydroxy half ester is 2 for propanoic acid and dihydroxy half ester:1), the fire retardant is for (N, N- are double
(2- ethoxys) aminomethy-lenephosphonic acids diethylester) and double (4- hydroxy phenyls) phenyl phosphine oxides ((double (2- ethoxys) ammonia of N, N-
Methylene diethyl phosphonate) and the mass ratio of double (4- hydroxy phenyls) phenyl phosphine oxide be 1:1), the nertralizer is five first
(mass ratio of pentamethyl-diethylenetriamine and N, N- dimethyl cyclohexyl amine is 1 for base diethylenetriamine and N, N- dimethyl cyclohexyl amine:
2)；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 45
Mix homogeneously under the conditions of DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 90 DEG C, question response add step one in reaction system after carrying out 4h
Described in organosilicon, continue reaction 3h after stop, obtaining performed polymer；NCO and step one in the polyisocyanates
Described in glycol composition the mol ratio of hydroxyl be 3:1；The polyisocyanates is toluene di-isocyanate(TDI) and different Fo Er
(mass ratio of toluene di-isocyanate(TDI) and isophorone diisocyanate is 2 to ketone diisocyanate:1), the catalyst is two
(mass ratio of dibutyl tin laurate and stannous octoate is 1 for dibutyl tin laurate and stannous octoate:1), the organosilicon
For KH-560 and KH-570, (mass ratio of KH-560 and KH-570 is 1:1)；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 5 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 35wt%.
From figure 2 it can be seen that hydrophobic flame-retardant polyurethane coating prepared by embodiment 3 is under the conditions of 263 DEG C and 285 DEG C
Weight-loss ratio respectively may be about 5% and 10%, determine the poly- ammonia of the hydrophobic flame retardant type using LFY-606B type digital display oxygen index measurers
The limited oxygen index of ester paint is 29, and according to UL94 standard tests, its fire resistance index can reach Vo ranks, using MCAT
It is 98 ° that type contact angle instrument determines the surface contact angle of the hydrophobic flame-retardant polyurethane coating, and water absorption rate is 1.7%, explanation
The hydrophobic flame-retardant polyurethane coating has good thermostability, anti-flammability and hydrophobicity.
Embodiment 4
The present embodiment is same as Example 3, and its difference is：Polymer polyatomic alcohol described in step one is poly- second two
One kind in alcohol, polypropylene glycol, polytetramethylene glycol, PTMG and poly(ethylene oxide) or more than three kinds, or be poly- second two
Two kinds in alcohol, polytetramethylene glycol, PTMG and poly(ethylene oxide), or for polytetramethylene glycol, PTMG and gather
A kind of mixture of the and polypropylene glycol in oxirane；The hydrophilic chain extender be dihydromethyl propionic acid, dihydroxy half ester and
It is a kind of or three kinds in diaminobenzoic acid, or be dihydromethyl propionic acid and diaminobenzoic acid, or be diaminobenzoic acid
With dihydroxy half ester；The fire retardant is (double (2- ethoxys) the aminomethy-lenephosphonic acids diethylesters of N, N-), double (4- hydroxy benzeness
Base) one kind in phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol, three kinds or four kinds, or for the (double (2- of N, N-
Ethoxy) aminomethy-lenephosphonic acids diethylester), two kinds in tetrabromo-benzene anhydride diol and dibromoneopentyl glycol, or be tetrabromo-benzene
The mixture of the one kind in acid anhydride glycol and dibromoneopentyl glycol and double (4- hydroxy phenyls) phenyl phosphine oxides；The nertralizer is five
Methyl diethylenetriamine, N, the one kind in N- dimethyl cyclohexyl amines, triethylene diamine and triethylamine or more than three kinds, or be five
Two kinds in methyl diethylenetriamine, triethylene diamine and triethylamine, or for the one kind in triethylene diamine and triethylamine with
The mixture of N, N- dimethyl cyclohexyl amine；
Polyisocyanates described in step 3 is toluene di-isocyanate(TDI), isophorone diisocyanate, diphenyl methane
One kind in diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer or more than three kinds, or
Person is toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, two Carbimide. of hexamethylene diisocyanate and hexa-methylene
Two kinds in ester trimer, or it is different for methyl diphenylene diisocyanate, hexamethylene diisocyanate and hexa-methylene two
A kind of mixture of the and isophorone diisocyanate in cyanate trimer；The catalyst is di lauric dibutyl
It is a kind of or three kinds in stannum, stannous octoate and three n-butylbenzoic acid stannum, or be dibutyl tin laurate and three n-butylbenzenes
Formic acid stannum, or be stannous octoate and three n-butylbenzoic acid stannum；During the organosilicon is KH-550, KH-560 and KH-570
It is a kind of or three kinds, or be KH-550 and KH-560, or be KH-550 and KH-570.
Hydrophobic flame-retardant polyurethane coating manufactured in the present embodiment has good thermostability, anti-flammability and hydrophobicity.
Embodiment 5
The present embodiment is comprised the following steps：
Step one, the various raw materials for weighing following weight portion：75 parts of polyhydric alcohol, 25 parts of fire retardant, 60 parts of solvent, hydrophilic expansion
11 parts of chain agent, 5.5 parts of nertralizer, 3 parts of catalyst, 20 parts of organosilicon；The glycol composition by biomass-based polyhydric alcohol and
Polymer polyatomic alcohol is mixed, and in the glycol composition, the mass content of biomass-based polyhydric alcohol is 13.3%, surplus
For polymer polyatomic alcohol；The biomass-based polyhydric alcohol is hydroxypropyl cyclodextrin, and the polymer polyatomic alcohol is Polyethylene Glycol, poly-
(mass ratio of Polyethylene Glycol, polypropylene glycol and polytetramethylene glycol is 1 for Propylene Glycol and polytetramethylene glycol:1:1)；The solvent is acetone,
The hydrophilic chain extender is dihydromethyl propionic acid, dihydroxy half ester and diaminobenzoic acid (dihydromethyl propionic acid, dihydroxy half ester
Mass ratio with diaminobenzoic acid is 1:2:1), the fire retardant is (double (2- ethoxys) aminomethy-lenephosphonic acids two of N, N-
Ethyl ester), double (4- hydroxy phenyls) phenyl phosphine oxides and tetrabromo-benzene anhydride diol ((double (2- ethoxys) aminomethy-lenephosphonic acids of N, N-
Diethylester), the mass ratio of double (4- hydroxy phenyls) phenyl phosphine oxides and tetrabromo-benzene anhydride diol be 1:1:2), the nertralizer is five
Methyl diethylenetriamine, N, N- dimethyl cyclohexyl amines and triethylene diamine (pentamethyl-diethylenetriamine, N, N- dimethyl cyclohexyl amines
Mass ratio with triethylene diamine is 1:2:1)；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 30
Mix homogeneously under the conditions of DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 50 DEG C, question response add step one in reaction system after carrying out 5h
Described in organosilicon, continue reaction 1h after stop, obtaining performed polymer；NCO and step one in the polyisocyanates
Described in glycol composition the mol ratio of hydroxyl be 3:1；The polyisocyanates is toluene di-isocyanate(TDI), isophorone
Diisocyanate, methyl diphenylene diisocyanate (toluene di-isocyanate(TDI), isophorone diisocyanate, diphenyl methane
The mass ratio of diisocyanate is 1:1:1), the catalyst is dibutyl tin laurate, stannous octoate and three n-butylbenzenes
(mass ratio of dibutyl tin laurate, stannous octoate and three n-butylbenzoic acid stannum is 2 to formic acid stannum:1:1), the organosilicon
For KH-550, KH-560 and KH-570, (mass ratio of KH-550, KH-560 and KH-570 is 1:1:1)；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 5 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 40wt%.
From figure 3, it can be seen that hydrophobic flame-retardant polyurethane coating prepared by embodiment 5 is under the conditions of 245 DEG C and 265 DEG C
Weight-loss ratio respectively may be about 5% and 10%, determine the poly- ammonia of the hydrophobic flame retardant type using LFY-606B type digital display oxygen index measurers
The limited oxygen index of ester paint is 29, and according to UL94 standard tests, its fire resistance index can reach Vo ranks, using MCAT
It is 87 ° that type contact angle instrument determines the surface contact angle of the hydrophobic flame-retardant polyurethane coating, and water absorption rate is 3.8%, explanation
The hydrophobic flame-retardant polyurethane coating has good thermostability, anti-flammability and hydrophobicity.
Embodiment 6
The present embodiment is same as Example 5, and its difference is：Polymer polyatomic alcohol described in step one is poly- second two
One kind in alcohol, polypropylene glycol, polytetramethylene glycol, PTMG and poly(ethylene oxide), two kinds or more than four kinds, or be poly-
Two kinds in a kind of and polytetramethylene glycol, PTMG and poly(ethylene oxide) in ethylene glycol, polypropylene glycol and polytetramethylene glycol
Mixture, or for two kinds in Polyethylene Glycol, polypropylene glycol and polytetramethylene glycol and polytetramethylene glycol, PTMG and poly-
A kind of mixture in oxirane, or be polytetramethylene glycol, PTMG and poly(ethylene oxide)；The hydrophilic chain extension
Agent be dihydromethyl propionic acid, dihydroxy half ester and diaminobenzoic acid in one or two；The fire retardant is for (N, N- are double
(2- ethoxys) aminomethy-lenephosphonic acids diethylester), double (4- hydroxy phenyls) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromos it is new
One kind in pentanediol, two kinds or four kinds, or for (double (2- ethoxys) the aminomethy-lenephosphonic acids diethylesters of N, N-), double (4-
Hydroxy phenyl) two kinds in phenyl phosphine oxide and tetrabromo-benzene anhydride diol with the mixture of dibromoneopentyl glycol；The nertralizer is
Pentamethyl-diethylenetriamine, N, one kind in N- dimethyl cyclohexyl amines, triethylene diamine and triethylamine, two kinds or four kinds, or
For pentamethyl-diethylenetriamine, N, the mixture of two in N- dimethyl cyclohexyl amines and triethylene diamine kind and triethylamine；
Polyisocyanates described in step 3 is toluene di-isocyanate(TDI), isophorone diisocyanate, diphenyl methane
One kind in diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer, two kinds or four kinds with
On, or for one kind in toluene di-isocyanate(TDI), isophorone diisocyanate and methyl diphenylene diisocyanate and six
The mixture of methylene diisocyanate, hexamethylene diisocyanate trimer, or be toluene di-isocyanate(TDI), different Fo Er
Two kinds in ketone diisocyanate and methyl diphenylene diisocyanate are different with hexamethylene diisocyanate and hexa-methylene two
A kind of mixture in cyanate trimer；The catalyst is dibutyl tin laurate, stannous octoate and three normal-butyls
In benzoic acid stannum one or two；The organosilicon be KH-550, KH-560 and KH-570 in one or two.
Hydrophobic flame-retardant polyurethane coating manufactured in the present embodiment has good thermostability, anti-flammability and hydrophobicity.
Embodiment 7
The present embodiment is comprised the following steps：
Step one, the various raw materials for weighing following weight portion：75 parts of polyhydric alcohol, 25 parts of fire retardant, 50 parts of solvent, hydrophilic expansion
10 parts of chain agent, 5 parts of nertralizer, 2.5 parts of catalyst, 10 parts of organosilicon；The glycol composition by biomass-based polyhydric alcohol and
Polymer polyatomic alcohol is mixed, and in the glycol composition, the mass content of biomass-based polyhydric alcohol is 13.3%, surplus
For polymer polyatomic alcohol；The biomass-based polyhydric alcohol is modified rosin, and the modified rosin is that Jing maleic acids and dihydroxylic alcohols change
The Colophonium of property；The polymer polyatomic alcohol be Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol and PTMG (Polyethylene Glycol,
The mass ratio of polypropylene glycol, polytetramethylene glycol and PTMG is 1:2:1:2)；The solvent be acetone, the hydrophilic chain extension
Agent N methyldiethanol amine, the fire retardant are (double (2- ethoxys) the aminomethy-lenephosphonic acids diethylesters of N, N-), double (4- hydroxyls
Phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol ((double (2- ethoxys) aminomethy-lenephosphonic acids two of N, N-
Ethyl ester), the mass ratio of double (4- hydroxy phenyls) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycols be 2:2:1:1),
The nertralizer is acetic acid；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 45
Mix homogeneously under the conditions of DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 70 DEG C, question response add step one in reaction system after carrying out 6h
Described in organosilicon, continue reaction 3h after stop, obtaining performed polymer；NCO and step one in the polyisocyanates
Described in glycol composition the mol ratio of hydroxyl be 1.1:1；The polyisocyanates is toluene di-isocyanate(TDI), different Fo Er
Ketone diisocyanate, methyl diphenylene diisocyanate and hexamethylene diisocyanate (toluene di-isocyanate(TDI), isophorone
The mass ratio of diisocyanate, methyl diphenylene diisocyanate and hexamethylene diisocyanate is 1:1:1:1) it is, described to urge
Agent is stannous octoate, and the organosilicon is KH-560；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 2 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 30wt%.
Figure 4, it is seen that hydrophobic flame-retardant polyurethane coating prepared by embodiment 7 is under the conditions of 252 DEG C and 285 DEG C
Weight-loss ratio respectively may be about 5% and 10%, determine the poly- ammonia of the hydrophobic flame retardant type using LFY-606B type digital display oxygen index measurers
The limited oxygen index of ester paint is 28, and according to UL94 standard tests, its fire resistance index can reach Vo ranks, using MCAT
It is 96 ° that type contact angle instrument determines the surface contact angle of the hydrophobic flame-retardant polyurethane coating, and water absorption rate is 1.1%, explanation
The hydrophobic flame-retardant polyurethane coating has good thermostability, anti-flammability and hydrophobicity.
Embodiment 8
The present embodiment is same as Example 7, and its difference is：Polymer polyatomic alcohol described in step one is poly- second two
One kind in alcohol, polypropylene glycol, polytetramethylene glycol, PTMG and poly(ethylene oxide), two kinds, three kinds or five kinds, Huo Zhewei
The mixture of three kinds in Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol and PTMG and poly(ethylene oxide)；It is described fire-retardant
Agent is (double (2- ethoxys) the aminomethy-lenephosphonic acids diethylesters of N, N-), double (4- hydroxy phenyls) phenyl phosphine oxides, PHT4
One kind in glycol and dibromoneopentyl glycol, two or three；
Polyisocyanates described in step 3 is toluene di-isocyanate(TDI), isophorone diisocyanate, diphenyl methane
One kind in diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer, two kinds, three kinds or five
Kind, or be toluene di-isocyanate(TDI), isophorone diisocyanate and methyl diphenylene diisocyanate for polyisocyanates
In two kinds with hexamethylene diisocyanate, the mixture of hexamethylene diisocyanate trimer.
Hydrophobic flame-retardant polyurethane coating manufactured in the present embodiment has good thermostability, anti-flammability and hydrophobicity.
Embodiment 9
The present embodiment is comprised the following steps：
Step one, the various raw materials for weighing following weight portion：20 parts of polyhydric alcohol, 5 parts of fire retardant, 20 parts of solvent, hydrophilic expansion
5 parts of chain agent, 5 parts of nertralizer, 0.05 part of catalyst, 15 parts of organosilicon；The glycol composition by biomass-based polyhydric alcohol and
Polymer polyatomic alcohol is mixed, and in the glycol composition, the mass content of biomass-based polyhydric alcohol is 10%, balance of
Polymer polyatomic alcohol；The biomass-based polyhydric alcohol is modified rosin, and the modified rosin is Jing maleic acids and glycol modified
Colophonium；The polymer polyatomic alcohol is Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol, PTMG and poly(ethylene oxide)
(mass ratio of Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol, PTMG and poly(ethylene oxide) is 2:1:1:2:1)；It is described
Solvent is acetone, and the hydrophilic chain extender is dihydromethyl propionic acid, and the fire retardant is double (4- hydroxy phenyls) phenyl phosphine oxides,
The nertralizer be pentamethyl-diethylenetriamine, N, N- dimethyl cyclohexyl amines, triethylene diamine and triethylamine (pentamethyl divinyl
Triamine, N, the mass ratio of N- dimethyl cyclohexyl amines, triethylene diamine and triethylamine is 1:1:1:1)；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 30
Mix homogeneously under the conditions of DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 50 DEG C, question response add step after carrying out 10h in reaction system
Organosilicon described in one, stops after continuing reaction 2h, obtains performed polymer；NCO and step in the polyisocyanates
Described in one, in glycol composition, the mol ratio of hydroxyl is 2:1；The polyisocyanates is toluene di-isocyanate(TDI), different Fo Er
Ketone diisocyanate, methyl diphenylene diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimerization
Body (toluene di-isocyanate(TDI), isophorone diisocyanate, methyl diphenylene diisocyanate, hexamethylene diisocyanate
Mass ratio with hexamethylene diisocyanate trimer is 1:1:2:1:1), the catalyst is three n-butylbenzoic acid stannum,
The organosilicon is KH-570；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 20wt%.
The weight-loss ratio of hydrophobic flame-retardant polyurethane coating prepared by embodiment 9 under the conditions of 212 DEG C and 239 DEG C respectively may be about
5% and 10%, the limit oxygen for determining the hydrophobic flame-retardant polyurethane coating using LFY-606B type digital display oxygen index measurers refers to
Number is 28, and according to UL94 standard tests, its fire resistance index can reach Vo ranks, is surveyed using MCAT types contact angle instrument
The surface contact angle of the fixed hydrophobic flame-retardant polyurethane coating is 93 °, and water absorption rate is 1.4%, illustrates the poly- ammonia of the hydrophobic flame retardant type
Ester paint has good thermostability, anti-flammability and hydrophobicity.
Embodiment 10
The present embodiment is same as Example 9, and its difference is：Polymer polyatomic alcohol described in step one is poly- second two
Less than four kinds in alcohol, polypropylene glycol, polytetramethylene glycol, PTMG and poly(ethylene oxide)；The nertralizer is pentamethyl
Diethylenetriamine, N, one kind in N- dimethyl cyclohexyl amines, triethylene diamine and triethylamine, two or three；
Polyisocyanates described in step 3 is toluene di-isocyanate(TDI), isophorone diisocyanate, diphenyl methane
Less than four kinds in diisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer.
Hydrophobic flame-retardant polyurethane coating manufactured in the present embodiment has good thermostability, anti-flammability and hydrophobicity.
Embodiment 11
The present embodiment is comprised the following steps：
Step one, the various raw materials for weighing following weight portion：90 parts of polyhydric alcohol, 40 parts of fire retardant, 60 parts of solvent, hydrophilic expansion
30 parts of chain agent, 50 parts of nertralizer, 3 parts of catalyst, 30 parts of organosilicon；The glycol composition is by biomass-based polyhydric alcohol and gathers
Compound polyhydric alcohol is mixed, and in the glycol composition, the mass content of biomass-based polyhydric alcohol is 25%, balance of poly-
Compound polyhydric alcohol；The biomass-based polyhydric alcohol is hydroxyethyl cyclodextrin；The polymer polyatomic alcohol is polycaprolactone；It is described molten
Agent is acetone, the hydrophilic chain extender dihydroxy half ester, and the fire retardant is tetrabromo-benzene anhydride diol, and the nertralizer is triethylene
Diamidogen；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 60
Mix homogeneously under the conditions of DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 80 DEG C, question response add step one in reaction system after carrying out 9h
Described in organosilicon, continue reaction 2h after stop, obtaining performed polymer；NCO and step one in the polyisocyanates
Described in glycol composition the mol ratio of hydroxyl be 1.5:1；The polyisocyanates is methyl diphenylene diisocyanate,
The catalyst is stannous octoate, and the organosilicon is KH-550；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 5 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 55%.
The weight-loss ratio of hydrophobic flame-retardant polyurethane coating prepared by embodiment 11 under the conditions of 260 DEG C and 281 DEG C is respectively about
For 5% and 10%, the limit oxygen of the hydrophobic flame-retardant polyurethane coating is determined using LFY-606B type digital display oxygen index measurers
Index is 29, and according to UL94 standard tests, its fire resistance index can reach Vo ranks, using MCAT type contact angle instruments
The surface contact angle for determining the hydrophobic flame-retardant polyurethane coating is 101 °, and water absorption rate is 0.9%, illustrates that the hydrophobic flame retardant type gathers
Urethane coating has good thermostability, anti-flammability and hydrophobicity.
Embodiment 12
The present embodiment is identical with embodiment 11, and its difference is：Polymer polyatomic alcohol described in step one is poly- right
Benzene dicarboxylic acid butanediol ester, polyethylene terephthalate or polyadipate-BDO ester, or for polycaprolactone,
In polybutylene terephthalate (PBT), polyethylene terephthalate and polyadipate -1,4- butanediol esters at least two.
Hydrophobic flame-retardant polyurethane coating manufactured in the present embodiment has good thermostability, anti-flammability and hydrophobicity.
Embodiment 13
The present embodiment is comprised the following steps：
Step one, the various raw materials for weighing following weight portion：80 parts of polyhydric alcohol, 30 parts of fire retardant, 50 parts of solvent, hydrophilic expansion
20 parts of chain agent, 40 parts of nertralizer, 2.5 parts of catalyst, 25 parts of organosilicon；The glycol composition by biomass-based polyhydric alcohol and
Polymer polyatomic alcohol is mixed, and in the glycol composition, the mass content of biomass-based polyhydric alcohol is 20%, balance of
Polymer polyatomic alcohol；The biomass-based polyhydric alcohol is hydroxypropyl cyclodextrin；The polymer polyatomic alcohol is polycaprolactone and gathers
(mass ratio of polycaprolactone and polybutylene terephthalate (PBT) is 1 to mutual-phenenyl two acid bromide two alcohol ester:2)；The solvent is third
Ketone, the hydrophilic chain extender are diaminobenzoic acid, and the fire retardant is dibromoneopentyl glycol, and the nertralizer is triethylamine；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 40
Mix homogeneously under the conditions of DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 70 DEG C, question response add step one in reaction system after carrying out 8h
Described in organosilicon, continue reaction 2h after stop, obtaining performed polymer；NCO and step one in the polyisocyanates
Described in glycol composition the mol ratio of hydroxyl be 2:1；The polyisocyanates is hexamethylene diisocyanate, described
Catalyst is stannous octoate, and the organosilicon is KH-560；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 40wt%.
The weight-loss ratio of hydrophobic flame-retardant polyurethane coating prepared by embodiment 13 under the conditions of 255 DEG C and 274 DEG C is respectively about
For 5% and 10%, the limit oxygen of the hydrophobic flame-retardant polyurethane coating is determined using LFY-606B type digital display oxygen index measurers
Index is 30, and according to UL94 standard tests, its fire resistance index can reach Vo ranks, using MCAT type contact angle instruments
The surface contact angle for determining the hydrophobic flame-retardant polyurethane coating is 97 °, and water absorption rate is 1.3%, illustrates that the hydrophobic flame retardant type gathers
Urethane coating has good thermostability, anti-flammability and hydrophobicity.
Embodiment 14
The present embodiment is identical with embodiment 13, and its difference is：Polymer polyatomic alcohol described in step one is poly- right
Benzene dicarboxylic acid butanediol ester, polyethylene terephthalate or polyadipate-BDO ester, or for polycaprolactone,
One kind or three in polybutylene terephthalate (PBT), polyethylene terephthalate and polyadipate -1,4- butanediol esters
More than kind, or for two kinds in polycaprolactone, polyethylene terephthalate and polyadipate-BDO ester, or
Person is the one kind and polybutylene terephthalate (PBT) in polyethylene terephthalate and polyadipate -1,4- butanediol esters
Mixture.
Hydrophobic flame-retardant polyurethane coating manufactured in the present embodiment has good thermostability, anti-flammability and hydrophobicity.
Embodiment 15
The present embodiment is comprised the following steps：
Step one, the various raw materials for weighing following weight portion：30 parts of polyhydric alcohol, 10 parts of fire retardant, 30 parts of solvent, hydrophilic expansion
5 parts of chain agent, 10 parts of nertralizer, 1 part of catalyst, 5 parts of organosilicon；The glycol composition is by biomass-based polyhydric alcohol and polymerization
Thing polyhydric alcohol is mixed, and in the glycol composition, the mass content of biomass-based polyhydric alcohol is 15.6%, balance of poly-
Compound polyhydric alcohol；The biomass-based polyhydric alcohol is hydroxypropyl cyclodextrin；The polymer polyatomic alcohol is polycaprolactone, gathers to benzene
Dioctyl phthalate butanediol ester and polyethylene terephthalate (polycaprolactone, polybutylene terephthalate (PBT) and poly- to benzene two
The mass ratio of formic acid glycol ester is 1:1:1)；The solvent is acetone, and the hydrophilic chain extender is diaminobenzoic acid, described
Fire retardant is dibromoneopentyl glycol, and the nertralizer is triethylamine；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 30
Mix homogeneously under the conditions of DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 60 DEG C, question response add step one in reaction system after carrying out 6h
Described in organosilicon, continue reaction 1h after stop, obtaining performed polymer；NCO and step one in the polyisocyanates
Described in glycol composition the mol ratio of hydroxyl be 1.3:1；The polyisocyanates be isophorone diisocyanate, institute
It is dibutyl tin laurate to state catalyst, and the organosilicon is KH-560；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 3 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 25wt%.
The weight-loss ratio of hydrophobic flame-retardant polyurethane coating prepared by embodiment 15 under the conditions of 232 DEG C and 260 DEG C is respectively about
For 5% and 10%, the limit oxygen of the hydrophobic flame-retardant polyurethane coating is determined using LFY-606B type digital display oxygen index measurers
Index is 29, and according to UL94 standard tests, its fire resistance index can reach Vo ranks, using MCAT type contact angle instruments
The surface contact angle for determining the hydrophobic flame-retardant polyurethane coating is 92 °, and water absorption rate is 1.6%, illustrates that the hydrophobic flame retardant type gathers
Urethane coating has good thermostability, anti-flammability and hydrophobicity.
Embodiment 16
The present embodiment is identical with embodiment 15, and its difference is：Polymer polyatomic alcohol described in step one is poly- right
Benzene dicarboxylic acid butanediol ester, polyethylene terephthalate or polyadipate-BDO ester, or for polycaprolactone,
One kind in polybutylene terephthalate (PBT), polyethylene terephthalate and polyadipate -1,4- butanediol esters, two kinds
Or four kinds, or for two kinds in polycaprolactone, polybutylene terephthalate (PBT) and polyethylene terephthalate with it is poly-
The mixture of adipic acid -1,4- butanediol esters.
Hydrophobic flame-retardant polyurethane coating manufactured in the present embodiment has good thermostability, anti-flammability and hydrophobicity.
Embodiment 17
The present embodiment is comprised the following steps：
Step one, the various raw materials for weighing following weight portion：55 parts of polyhydric alcohol, 24 parts of fire retardant, 40 parts of solvent, hydrophilic expansion
18 parts of chain agent, 28 parts of nertralizer, 0.08 part of catalyst, 15 parts of organosilicon；The glycol composition is by biomass-based polyhydric alcohol
Mix with polymer polyatomic alcohol, in the glycol composition, the mass content of biomass-based polyhydric alcohol is 22%, surplus
For polymer polyatomic alcohol；The biomass-based polyhydric alcohol is hydroxypropyl cyclodextrin；The polymer polyatomic alcohol is polycaprolactone, gathers
Mutual-phenenyl two acid bromide two alcohol ester, polyethylene terephthalate and polyadipate -1,4- butanediol esters are (polycaprolactone, poly- right
The mass ratio of benzene dicarboxylic acid butanediol ester, polyethylene terephthalate and polyadipate -1,4- butanediol esters is 1:2:1:
2)；The solvent is acetone, and the hydrophilic chain extender is dihydromethyl propionic acid, and the fire retardant is for (N, N- are double (2- ethoxys)
Aminomethy-lenephosphonic acids diethylester), the nertralizer be N, N- dimethyl cyclohexyl amines；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 45
Mix homogeneously under the conditions of DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then
The stirring reaction under the nitrogen atmosphere protective condition that temperature is 70 DEG C, question response add step one in reaction system after carrying out 6h
Described in organosilicon, continue reaction 2h after stop, obtaining performed polymer；NCO and step one in the polyisocyanates
Described in glycol composition the mol ratio of hydroxyl be 1.6:1；The polyisocyanates is methyl diphenylene diisocyanate,
The catalyst is dibutyl tin laurate, and the organosilicon is KH-550；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 30wt%.
The weight-loss ratio of hydrophobic flame-retardant polyurethane coating prepared by embodiment 17 under the conditions of 243 DEG C and 276 DEG C is respectively about
For 5% and 10%, the limit oxygen of the hydrophobic flame-retardant polyurethane coating is determined using LFY-606B type digital display oxygen index measurers
Index is 28, and according to UL94 standard tests, its fire resistance index can reach Vo ranks, using MCAT type contact angle instruments
The surface contact angle for determining the hydrophobic flame-retardant polyurethane coating is 99 °, and water absorption rate is 0.7%, illustrates that the hydrophobic flame retardant type gathers
Urethane coating has good thermostability, anti-flammability and hydrophobicity.
Embodiment 18
The present embodiment is identical with embodiment 17, and its difference is：Polymer polyatomic alcohol described in step one is poly- right
One kind in benzene dicarboxylic acid butanediol ester, polyethylene terephthalate and polyadipate -1,4- butanediol esters, two kinds or three
Kind.
Hydrophobic flame-retardant polyurethane coating manufactured in the present embodiment has good thermostability, anti-flammability and hydrophobicity.
The above, is only presently preferred embodiments of the present invention, not the present invention is imposed any restrictions, every according to the present invention
Any simple modification, change and equivalent structure change that technical spirit is made to above example, still fall within skill of the present invention
In the protection domain of art scheme.
Claims (9)
1. a kind of preparation method of hydrophobic flame-retardant polyurethane coating, it is characterised in that comprise the following steps：
Step one, the various raw materials for weighing following weight portion：20～90 parts of glycol composition, 5～40 parts of fire retardant, solvent 20
～60 parts, 5～30 parts of hydrophilic chain extender, 5～50 parts of nertralizer, 0.05～3 part of catalyst, 5～30 parts of organosilicon；It is described polynary
Alcohol composition is mixed by biomass-based polyhydric alcohol and polymer polyatomic alcohol, biomass-based polynary in the glycol composition
The mass content of alcohol is 10%～25%, balance of polymer polyatomic alcohol；The biomass-based polyhydric alcohol is modified rosin or hydroxyl
Alkylated cyclodextrin, the polymer polyatomic alcohol are PEPA or polyether polyol, and the solvent is acetone；It is described modified
Colophonium is Jing maleic acids and glycol modified Colophonium, and the hydroxyalkylated cyclodextrins are that hydroxypropyl cyclodextrin or ethoxy ring are pasted
Essence；The fire retardant is (double (2- ethoxys) the aminomethy-lenephosphonic acids diethylesters of N, N-), the oxidation of double (4- hydroxy phenyls) phenyl
One or more in phosphine, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol；
Step 2, by glycol composition described in step one, fire retardant, solvent, hydrophilic chain extender and nertralizer 30 DEG C～
Mix homogeneously under the conditions of 60 DEG C, obtains mixture；
Step 3, to catalyst described in Deca polyisocyanates in mixture described in step 2 and step one, then in temperature
Stirring reaction under the nitrogen atmosphere protective condition for 50 DEG C～90 DEG C is spent, question response adds after carrying out 4h～10h in reaction system
Enter organosilicon described in step one, stop after continuing reaction 1h～3h, obtain performed polymer；Carbimide. in the polyisocyanates
Described in ester group and step one, in glycol composition, the mol ratio of hydroxyl is (1.1～3):1；
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C～5 DEG C, the Deca water in the performed polymer, in stirring
Under the conditions of emulsifying is carried out to performed polymer, then evacuation remove solvent, obtain hydrophobic flame-retardant polyurethane coating；The matter of the water
Amount consumption be make the hydrophobic flame-retardant polyurethane coating solid content be 20wt%～55wt%.
2. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating described in claim 1, it is characterised in that step one
Middle weighed various raw materials are respectively：30～80 parts of glycol composition, 10～30 parts of fire retardant, 30～50 parts of solvent, parent
5～20 parts of water chain extender, 10～40 parts of nertralizer, 1～3 part of catalyst, 5～25 parts of organosilicon.
3. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating described in claim 2, it is characterised in that weighed
Various raw materials be respectively：80 parts of polyhydric alcohol, 20 parts of fire retardant, 40 parts of solvent, 5 parts of hydrophilic chain extender, 10 parts of nertralizer, catalysis
3 parts of agent, 5 parts of organosilicon.
4. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating described in claim 1, it is characterised in that step one
Described in hydrophilic chain extender be dihydromethyl propionic acid, dihydroxy half ester and diaminobenzoic acid in one or more；Institute
Nertralizer is stated for pentamethyl-diethylenetriamine, N, one or two in N- dimethyl cyclohexyl amines, triethylene diamine and triethylamine
More than.
5. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating described in claim 1, it is characterised in that step one
Described in hydrophilic chain extender be N methyldiethanol amine, the nertralizer be acetic acid.
6. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating described in claim 1, it is characterised in that step one
Described in PEPA be polycaprolactone, polybutylene terephthalate (PBT), polyethylene terephthalate and gather oneself two
One or more in acid -1,4- butanediol esters；The polyether polyol be Polyethylene Glycol, polypropylene glycol, polytetramethylene glycol,
One or more in PTMG and poly(ethylene oxide).
7. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating described in claim 1, it is characterised in that step 3
Described in polyisocyanates be toluene di-isocyanate(TDI), isophorone diisocyanate, methyl diphenylene diisocyanate, six sub-
One or more in methyl diisocyanate and hexamethylene diisocyanate trimer.
8. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating described in claim 1, it is characterised in that step 3
Described in catalyst be dibutyl tin laurate, stannous octoate and three n-butylbenzoic acid stannum in one or more.
9. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating described in claim 1, it is characterised in that step 3
Described in organosilicon be KH-550, KH-560 and KH-570 in one or more.
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| CN106750175A (en) * | 2017-01-18 | 2017-05-31 | 中国科学院长春应用化学研究所 | A kind of flame-retardant aqueous polyurethane and preparation method thereof, adhesive and preparation method thereof |
| CN108976370A (en) * | 2018-06-27 | 2018-12-11 | 滁州环球聚氨酯科技有限公司 | A kind of hydrophobic fire-retardant method for preparing polyurethane elastic body |
| CN109486378B (en) * | 2018-11-07 | 2020-08-04 | 苏州太湖电工新材料股份有限公司 | ATF oil-resistant flame-retardant insulating paint for electric automobile and preparation method and application thereof |
| NL2022275B1 (en) * | 2018-12-21 | 2020-07-15 | Stahl Int B V | Process to prepare halogen-free, flame-retardant aqueous polyurethane dispersions |
| CN110343457A (en) * | 2019-07-26 | 2019-10-18 | 株洲飞鹿高新材料技术股份有限公司 | A kind of steel construction automatically cleaning, fire prevention multifunctional coating and preparation method |
| CN113817399A (en) * | 2021-09-24 | 2021-12-21 | 肇庆市海特复合材料技术研究院 | Preparation method of flame-retardant polyurethane coating |
| CN114716896A (en) * | 2022-03-10 | 2022-07-08 | 浙江中聚材料有限公司 | High-heat-insulation flame-retardant paint and preparation method and application thereof |
| CN114716899A (en) * | 2022-03-30 | 2022-07-08 | 浙江中聚材料有限公司 | Flame-retardant coating with high flame-retardant stability, and preparation method and application thereof |
| CN116330793B (en) * | 2023-03-14 | 2023-09-26 | 南通北风橡塑制品有限公司 | High-temperature-resistant flame-retardant polyurethane composite board and processing technology thereof |
| CN116574440B (en) * | 2023-04-26 | 2024-01-19 | 广州市百庄复合材料有限公司 | Water-based protective agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101381445B (en) * | 2008-10-31 | 2011-08-17 | 北京理工大学 | Environment friendly non-halogen reacting fire-retardant aqueous polyurethane and preparation method thereof |
| CN101497685A (en) * | 2009-02-23 | 2009-08-05 | 中国林业科学研究院林产化学工业研究所 | Production of rosin based aqueous polyurethanes |
| CN102241942B (en) * | 2011-06-30 | 2013-06-19 | 江苏中科金龙化工有限公司 | Poly(propylene carbonate)-based polyurethane fireproof coating and preparation method thereof |
| CN102643531B (en) * | 2012-04-25 | 2014-08-13 | 辽宁工程技术大学 | Self-temperature-limited polyurethane grouting material and preparation method thereof |
| CN103289632B (en) * | 2013-06-15 | 2014-12-31 | 武汉方成科技新材料有限公司 | Single-component solvent-free polyurethane adhesive and preparation method thereof |
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