CN104893539A - 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, be specifically related to a kind of preparation method of hydrophobic flame-retardant polyurethane coating.
Background technology
Urethane is widely used in the fields such as paper-making industry, building coating, sizing agent, ink and leather.The polyurethane material major part of current use is inflammable material, and in today that fire takes place frequently, exploitation Flame retardant polyurethane material becomes the focus in epoch.Although the mode of being added fire retardant by physics can give material certain flame retardant properties, but fire retardant and polymer compatibility poor, easy migration or precipitate into material surface, destroy material mechanical performance, therefore, in the structural framework of synthesis of polyurethane material, introduce flame-retardant composition, give material intrinsic flame retardant properties, become the focus of Recent study.
Aqueous polyurethane coating is compared with solvent based coating, there is environment-protecting asepsis and pollute little advantage, but due to the molecular chain of aqueous polyurethane coating introducing hydrophilic radical, polar group in the water absorbed and urethane works, define hydrogen bond, reduce the effect of the hydrogen bond between polyurethane molecular, the physical strength of coating is reduced, makes polyurethane coating have significant limitation in actual applications.Therefore, improve flame retardant properties and the surface property of polyurethane material simultaneously, improve its water tolerance, the aqueous polyurethane coating obtaining high comprehensive performance becomes everybody common target.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned deficiency of the prior art, a kind of preparation method of hydrophobic flame-retardant polyurethane coating is provided, the method can improve the utilising efficiency of natural reproducible resource cyclodextrin and rosin, rigid annular structure is introduced in urethane, overcome existing aqueous polyurethane coating water tolerance, thermotolerance and the poor shortcoming of surface property, by introducing fire-retardant segment in polyurethane skeleton structure, synthesis eigenmode flame retardant polyurethane coating, overcome the shortcoming of additive flame flame-retardant polyurethane bad mechanical property, and utilize organic-silicon-modified, overcome the shortcoming of aqueous polyurethane coating poor water resistance further, obtain stablizing the polyurethane coating deposited, improve the over-all properties of polyurethane coating.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of hydrophobic flame-retardant polyurethane coating, is characterized in that, comprise the following steps:
Step one, take the various raw materials of following weight part: polyhydric alcohol composition 20 ~ 90 parts, fire retardant 5 ~ 40 parts, solvent 20 ~ 60 parts, hydrophilic chain extender 5 ~ 30 parts, neutralizing agent 5 ~ 50 parts, catalyzer 0.05 ~ 3 part, organosilicon 5 ~ 30 parts; Described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 10% ~ 25%, and surplus is polymer polyatomic alcohol; Described biomass-based polyvalent alcohol is modified rosin or hydroxyalkylated cyclodextrins, and described polymer polyatomic alcohol is polyester polyol or polyether glycol, and described solvent is acetone;
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 30 DEG C ~ 60 DEG C conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then be stirring reaction under the nitrogen atmosphere protective condition of 50 DEG C ~ 90 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 4h ~ 10h, stop after continuing reaction 1h ~ 3h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, 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, in described performed polymer, drip water, under agitation emulsification is carried out to described performed polymer, then vacuumize and remove described solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 20wt% ~ 55wt%.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterized in that, the various raw materials taken in step one are respectively: polyhydric alcohol composition 30 ~ 80 parts, fire retardant 10 ~ 30 parts, solvent 30 ~ 50 parts, hydrophilic chain extender 5 ~ 20 parts, neutralizing agent 10 ~ 40 parts, catalyzer 1 ~ 3 part, organosilicon 5 ~ 25 parts.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, is characterized in that, the various raw materials taken are respectively: polyvalent alcohol 80 parts, fire retardant 20 parts, solvent 40 parts, hydrophilic chain extender 5 parts, neutralizing agent 10 parts, catalyzer 3 parts, organosilicon 5 parts.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, is characterized in that, hydrophilic chain extender described in step one is one or more in dimethylol propionic acid, dihydroxyl half ester and diaminobenzoic acid; Described neutralizing agent is one or more in pentamethyl-diethylenetriamine, N, N-dimethylcyclohexylamine, triethylene diamine and triethylamine.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterized in that, hydrophilic chain extender described in step one is N methyldiethanol amine, described neutralizing agent is acetic acid.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, is characterized in that, modified rosin described in step one is through toxilic acid and glycol modified rosin, and described hydroxyalkylated cyclodextrins is hydroxypropyl cyclodextrin or hydroxyethyl cyclodextrin; Described fire retardant is one or more in (N, N-two (2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester), two (4-hydroxy phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterized in that, polyester polyol described in step one is one or more in polycaprolactone, polybutylene terephthalate, polyethylene terephthalate and poly-hexanodioic acid-BDO ester; Described polyether glycol is one or more in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG and polyethylene oxide.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, it is characterized in that, polyisocyanates described in step 3 is one or more in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, is characterized in that, catalyzer described in step 3 is one or more in dibutyl tin laurate, stannous octoate and three n-butylbenzoic acid tin.
The preparation method of above-mentioned a kind of hydrophobic flame-retardant polyurethane coating, is characterized in that, organosilicon described in step 3 is one or more in KH-550, KH-560 and KH-570.
The present invention compared with prior art has the following advantages:
1, in the present invention, modified rosin and hydroxyalkylated cyclodextrins are under the prerequisite ensureing biomass (rosin or cyclodextrin) basic structure (rigid annular structure), to the modification that the molecular structure of biomass carries out to a certain degree, give the functional group that biological surface is new, can greatly increase the water-soluble of biomass, improve reactivity worth, simultaneously, the rigid backbone of modified rosin or hydroxyalkylated cyclodextrins is introduced in polyurethane structural, can improve the water tolerance of urethane, glossiness and solvent resistant corrodibility.
2, the present invention can improve the utilising efficiency of natural reproducible resource cyclodextrin and rosin, rigid annular structure is introduced in urethane, overcome existing aqueous polyurethane coating water tolerance, thermotolerance and the poor shortcoming of surface property, by introducing fire-retardant segment in polyurethane skeleton structure, synthesis eigenmode flame retardant polyurethane coating, overcome the shortcoming of additive flame flame-retardant polyurethane bad mechanical property, and utilize organic-silicon-modified, overcome the shortcoming of aqueous polyurethane coating poor water resistance further, obtain stablizing the polyurethane coating deposited, improve the over-all properties of polyurethane coating.
3, fire retardant used in the present invention is while playing fire retardation, chainextender can also be served as in polyurethane molecular chain structure, the intrinsic being conducive to realizing urethane is fire-retardant, do not weaken its mechanical property simultaneously, the limiting oxygen index(LOI) of hydrophobic flame-retardant polyurethane prepared by the present invention is all 28 and above (ASTM D2863 standard testing result), reach Vo rank (UL94 standard test result), there is good flame retardant effect.
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Accompanying drawing explanation
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.
Embodiment
Embodiment 1
The present embodiment comprises the following steps:
Step one, take the various raw materials of following weight part: polyvalent alcohol 80 parts, fire retardant 20 parts, solvent 40 parts, hydrophilic chain extender 5 parts, neutralizing agent 10 parts, catalyzer 3 parts, organosilicon 5 parts; Described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 12.5%, and surplus is polymer polyatomic alcohol; Described biomass-based polyvalent alcohol is hydroxypropyl cyclodextrin, and described polymer polyatomic alcohol is polyoxyethylene glycol; Described solvent is acetone, and described hydrophilic chain extender is dimethylol propionic acid, and described fire retardant is (two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N, N-), and described neutralizing agent is pentamethyl-diethylenetriamine;
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 60 DEG C of conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then stirring reaction under the nitrogen atmosphere protective condition being 75 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 4h, stop after continuing reaction 1h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, the mol ratio of hydroxyl is 2:1; Described polyisocyanates is tolylene diisocyanate, and described catalyzer is dibutyl tin laurate, and described organosilicon is KH-560;
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C, in described performed polymer, drip water, under agitation emulsification is carried out to performed polymer, then vacuumize removal solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 30wt%.
As can be seen from Figure 1, the rate of weight loss of hydrophobic flame-retardant polyurethane coating under 252 DEG C and 270 DEG C of conditions prepared by embodiment 1 is about 5% and 10% respectively, the limiting oxygen index(LOI) utilizing LFY-606B type digital display oxygen index measurer to measure this hydrophobic flame-retardant polyurethane coating is 28, Vo rank can be reached according to its flame retardant properties index of UL94 standard test, the surface contact angle utilizing MCAT type contact angle instrument to measure this hydrophobic flame-retardant polyurethane coating is 92 °, water-intake rate is 2.6%, illustrate that this hydrophobic flame-retardant polyurethane coating has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 2
The present embodiment is identical with embodiment 1, its difference is: polymer polyatomic alcohol described in step one is polypropylene glycol, polytetramethylene glycol, PTMG or polyethylene oxide, or is at least two kinds in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG and polyethylene oxide; Described hydrophilic chain extender is dihydroxyl half ester or diaminobenzoic acid, or is at least two kinds in dimethylol propionic acid, dihydroxyl half ester and diaminobenzoic acid; Described fire retardant is two (4-hydroxy phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol or dibromoneopentyl glycols, or be at least two kinds in (two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N, N-), two (4-hydroxy phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol; Described neutralizing agent is N, N-dimethylcyclohexylamine, triethylene diamine or triethylamine, or is at least two kinds in pentamethyl-diethylenetriamine, N, N-dimethylcyclohexylamine, triethylene diamine and triethylamine;
Polyisocyanates described in step 3 is isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate or hexamethylene diisocyanate trimer, or is at least two kinds in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer; Described catalyzer is stannous octoate or three n-butylbenzoic acid tin, or is at least two kinds in dibutyl tin laurate, stannous octoate and three n-butylbenzoic acid tin; Described organosilicon KH-550 or KH-570, or be at least two kinds in KH-550, KH-560 and KH-570.
Hydrophobic flame-retardant polyurethane coating prepared by the present embodiment has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 3
The present embodiment comprises the following steps:
Step one, take the various raw materials of following weight part: polyvalent alcohol 60 parts, fire retardant 15 parts, solvent 30 parts, hydrophilic chain extender 9 parts, neutralizing agent 5 parts, catalyzer 2 parts, organosilicon 30 parts, described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 16.7%, and surplus is polymer polyatomic alcohol, described biomass-based polyvalent alcohol is hydroxyethyl cyclodextrin, and described polymer polyatomic alcohol is polyoxyethylene glycol and polypropylene glycol (mass ratio of polyoxyethylene glycol and polypropylene glycol is 1:1), described solvent is acetone, described hydrophilic chain extender is dimethylol propionic acid and dihydroxyl half ester (mass ratio of dimethylol propionic acid and dihydroxyl half ester is 2:1), described fire retardant is (N, two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N-) and two (4-hydroxy phenyl) phenyl phosphine oxide ((N, two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N-) and the mass ratio of pair (4-hydroxy phenyl) phenyl phosphine oxide be 1:1), described neutralizing agent is pentamethyl-diethylenetriamine and N, N-dimethylcyclohexylamine (pentamethyl-diethylenetriamine and N, the mass ratio of N-dimethylcyclohexylamine is 1:2),
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 45 DEG C of conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then stirring reaction under the nitrogen atmosphere protective condition being 90 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 4h, stop after continuing reaction 3h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, the mol ratio of hydroxyl is 3:1; Described polyisocyanates is tolylene diisocyanate and isophorone diisocyanate (mass ratio of tolylene diisocyanate and isophorone diisocyanate is 2:1), described catalyzer is dibutyl tin laurate and stannous octoate (mass ratio of dibutyl tin laurate and stannous octoate is 1:1), and described organosilicon is 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, in described performed polymer, drip water, under agitation emulsification is carried out to performed polymer, then vacuumize removal solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 35wt%.
As can be seen from Figure 2, the rate of weight loss of hydrophobic flame-retardant polyurethane coating under 263 DEG C and 285 DEG C of conditions prepared by embodiment 3 is about 5% and 10% respectively, the limiting oxygen index(LOI) utilizing LFY-606B type digital display oxygen index measurer to measure this hydrophobic flame-retardant polyurethane coating is 29, Vo rank can be reached according to its flame retardant properties index of UL94 standard test, the surface contact angle utilizing MCAT type contact angle instrument to measure this hydrophobic flame-retardant polyurethane coating is 98 °, water-intake rate is 1.7%, illustrate that this hydrophobic flame-retardant polyurethane coating has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 4
The present embodiment is identical with embodiment 3, its difference is: polymer polyatomic alcohol described in step one is one in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG and polyethylene oxide or more than three kinds, or be two kinds in polyoxyethylene glycol, polytetramethylene glycol, PTMG and polyethylene oxide, or be the mixture of a kind of and polypropylene glycol in polytetramethylene glycol, PTMG and polyethylene oxide; Described hydrophilic chain extender is a kind of in dimethylol propionic acid, dihydroxyl half ester and diaminobenzoic acid or three kinds, or is dimethylol propionic acid and diaminobenzoic acid, or is diaminobenzoic acid and dihydroxyl half ester; Described fire retardant is (N, two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N-), one in two (4-hydroxy phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol, three kinds or four kinds, or be (N, two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N-), in tetrabromo-benzene anhydride diol and dibromoneopentyl glycol two kinds, or be the one in tetrabromo-benzene anhydride diol and dibromoneopentyl glycol and the mixture of pair (4-hydroxy phenyl) phenyl phosphine oxide; Described neutralizing agent is pentamethyl-diethylenetriamine, N, one in N-dimethylcyclohexylamine, triethylene diamine and triethylamine or more than three kinds, or be two kinds in pentamethyl-diethylenetriamine, triethylene diamine and triethylamine, or be the mixture of one in triethylene diamine and triethylamine and N, N-dimethylcyclohexylamine;
Polyisocyanates described in step 3 is tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, one in hexamethylene diisocyanate and hexamethylene diisocyanate trimer or more than three kinds, or be tolylene diisocyanate, diphenylmethanediisocyanate, two kinds in hexamethylene diisocyanate and hexamethylene diisocyanate trimer, or be diphenylmethanediisocyanate, the mixture of a kind of and isophorone diisocyanate in hexamethylene diisocyanate and hexamethylene diisocyanate trimer, described catalyzer is a kind of in dibutyl tin laurate, stannous octoate and three n-butylbenzoic acid tin or three kinds, or is dibutyl tin laurate and three n-butylbenzoic acid tin, or is stannous octoate and three n-butylbenzoic acid tin, described organosilicon is one in KH-550, KH-560 and KH-570 or three kinds, or is KH-550 and KH-560, or is KH-550 and KH-570.
Hydrophobic flame-retardant polyurethane coating prepared by the present embodiment has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 5
The present embodiment comprises the following steps:
Step one, take the various raw materials of following weight part: polyvalent alcohol 75 parts, fire retardant 25 parts, solvent 60 parts, hydrophilic chain extender 11 parts, neutralizing agent 5.5 parts, catalyzer 3 parts, organosilicon 20 parts, described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 13.3%, and surplus is polymer polyatomic alcohol, described biomass-based polyvalent alcohol is hydroxypropyl cyclodextrin, and described polymer polyatomic alcohol is polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol (mass ratio of polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol is 1:1:1), described solvent is acetone, described hydrophilic chain extender is dimethylol propionic acid, dihydroxyl half ester and diaminobenzoic acid (dimethylol propionic acid, the mass ratio of dihydroxyl half ester and diaminobenzoic acid is 1:2:1), described fire retardant is (N, two (2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester of N-), two (4-hydroxy phenyl) phenyl phosphine oxide and tetrabromo-benzene anhydride diol ((N, two (2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester of N-), the mass ratio of two (4-hydroxy phenyl) phenyl phosphine oxide and tetrabromo-benzene anhydride diol is 1:1:2), described neutralizing agent is pentamethyl-diethylenetriamine, N, N-dimethylcyclohexylamine and triethylene diamine (pentamethyl-diethylenetriamine, N, the mass ratio of N-dimethylcyclohexylamine and triethylene diamine is 1:2:1),
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 30 DEG C of conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then stirring reaction under the nitrogen atmosphere protective condition being 50 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 5h, stop after continuing reaction 1h, obtain performed polymer, in polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, the mol ratio of hydroxyl is 3:1, described polyisocyanates is tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate (tolylene diisocyanate, isophorone diisocyanate, the mass ratio of diphenylmethanediisocyanate is 1:1:1), described catalyzer is dibutyl tin laurate, stannous octoate and three n-butylbenzoic acid tin (dibutyl tin laurates, the mass ratio of stannous octoate and three n-butylbenzoic acid tin is 2:1:1), described organosilicon is KH-550, KH-560 and KH-570 (KH-550, the mass ratio of 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, in described performed polymer, drip water, under agitation emulsification is carried out to performed polymer, then vacuumize removal solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 40wt%.
As can be seen from Figure 3, the rate of weight loss of hydrophobic flame-retardant polyurethane coating under 245 DEG C and 265 DEG C of conditions prepared by embodiment 5 is about 5% and 10% respectively, the limiting oxygen index(LOI) utilizing LFY-606B type digital display oxygen index measurer to measure this hydrophobic flame-retardant polyurethane coating is 29, Vo rank can be reached according to its flame retardant properties index of UL94 standard test, the surface contact angle utilizing MCAT type contact angle instrument to measure this hydrophobic flame-retardant polyurethane coating is 87 °, water-intake rate is 3.8%, illustrate that this hydrophobic flame-retardant polyurethane coating has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 6
The present embodiment is identical with embodiment 5, its difference is: polymer polyatomic alcohol described in step one is polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, one in PTMG and polyethylene oxide, more than two kinds or four kinds, or be polyoxyethylene glycol, one in polypropylene glycol and polytetramethylene glycol and polytetramethylene glycol, the mixture of two kinds in PTMG and polyethylene oxide, or be polyoxyethylene glycol, two kinds and polytetramethylene glycol in polypropylene glycol and polytetramethylene glycol, a kind of mixture in PTMG and polyethylene oxide, or be polytetramethylene glycol, PTMG and polyethylene oxide, described hydrophilic chain extender is one or both in dimethylol propionic acid, dihydroxyl half ester and diaminobenzoic acid, described fire retardant is (N, two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N-), one in two (4-hydroxy phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol, two kinds or four kinds, or be two kinds in (N, N-two (2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester), two (4-hydroxy phenyl) phenyl phosphine oxide and tetrabromo-benzene anhydride diol with the mixture of dibromoneopentyl glycol, described neutralizing agent is pentamethyl-diethylenetriamine, N, one in N-dimethylcyclohexylamine, triethylene diamine and triethylamine, two kinds or four kinds, or be two kinds in pentamethyl-diethylenetriamine, N, N-dimethylcyclohexylamine and triethylene diamine with the mixture of triethylamine,
Polyisocyanates described in step 3 is tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, one in hexamethylene diisocyanate and hexamethylene diisocyanate trimer, more than two kinds or four kinds, or be tolylene diisocyanate, one in isophorone diisocyanate and diphenylmethanediisocyanate and hexamethylene diisocyanate, the mixture of hexamethylene diisocyanate trimer, or be tolylene diisocyanate, two kinds in isophorone diisocyanate and diphenylmethanediisocyanate with a kind of mixture in hexamethylene diisocyanate and hexamethylene diisocyanate trimer, described catalyzer be in dibutyl tin laurate, stannous octoate and three n-butylbenzoic acid tin one or both, described organosilicon is one or both in KH-550, KH-560 and KH-570.
Hydrophobic flame-retardant polyurethane coating prepared by the present embodiment has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 7
The present embodiment comprises the following steps:
Step one, take the various raw materials of following weight part: polyvalent alcohol 75 parts, fire retardant 25 parts, solvent 50 parts, hydrophilic chain extender 10 parts, neutralizing agent 5 parts, catalyzer 2.5 parts, organosilicon 10 parts; Described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 13.3%, and surplus is polymer polyatomic alcohol; Described biomass-based polyvalent alcohol is modified rosin, and described modified rosin is through toxilic acid and glycol modified rosin; Described polymer polyatomic alcohol is polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and PTMG (mass ratio of polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and PTMG is 1:2:1:2); Described solvent is acetone, described hydrophilic chain extender N methyldiethanol amine, described fire retardant is (N, two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N-), two (4-hydroxy phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol ((N, two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N-), the mass ratio of two (4-hydroxy phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol is 2:2:1:1), described neutralizing agent is acetic acid;
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 45 DEG C of conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then stirring reaction under the nitrogen atmosphere protective condition being 70 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 6h, stop after continuing reaction 3h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, the mol ratio of hydroxyl is 1.1:1; Described polyisocyanates is tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate and hexamethylene diisocyanate (mass ratio of tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate and hexamethylene diisocyanate is 1:1:1:1), described catalyzer is stannous octoate, and described organosilicon is KH-560;
Step 4, treat that the temperature of performed polymer described in step 3 is down to 2 DEG C, in described performed polymer, drip water, under agitation emulsification is carried out to performed polymer, then vacuumize removal solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 30wt%.
As can be seen from Figure 4, the rate of weight loss of hydrophobic flame-retardant polyurethane coating under 252 DEG C and 285 DEG C of conditions prepared by embodiment 7 is about 5% and 10% respectively, the limiting oxygen index(LOI) utilizing LFY-606B type digital display oxygen index measurer to measure this hydrophobic flame-retardant polyurethane coating is 28, Vo rank can be reached according to its flame retardant properties index of UL94 standard test, the surface contact angle utilizing MCAT type contact angle instrument to measure this hydrophobic flame-retardant polyurethane coating is 96 °, water-intake rate is 1.1%, illustrate that this hydrophobic flame-retardant polyurethane coating has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 8
The present embodiment is identical with embodiment 7, its difference is: polymer polyatomic alcohol described in step one be one in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG and polyethylene oxide, two kinds, three kinds or five kinds, or be three kinds in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and PTMG with the mixture of polyethylene oxide; Described fire retardant is the one, two or three in (two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N, N-), two (4-hydroxy phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol;
Polyisocyanates described in step 3 be one in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer, two kinds, three kinds or five kinds, or for polyisocyanates be two kinds in tolylene diisocyanate, isophorone diisocyanate and diphenylmethanediisocyanate with the mixture of hexamethylene diisocyanate, hexamethylene diisocyanate trimer.
Hydrophobic flame-retardant polyurethane coating prepared by the present embodiment has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 9
The present embodiment comprises the following steps:
Step one, take the various raw materials of following weight part: polyvalent alcohol 20 parts, fire retardant 5 parts, solvent 20 parts, hydrophilic chain extender 5 parts, neutralizing agent 5 parts, catalyzer 0.05 part, organosilicon 15 parts; Described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 10%, and surplus is polymer polyatomic alcohol; Described biomass-based polyvalent alcohol is modified rosin, and described modified rosin is through toxilic acid and glycol modified rosin; Described polymer polyatomic alcohol is polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG and polyethylene oxide (mass ratio of polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG and polyethylene oxide is 2:1:1:2:1); Described solvent is acetone, described hydrophilic chain extender is dimethylol propionic acid, described fire retardant is two (4-hydroxy phenyl) phenyl phosphine oxides, described neutralizing agent is pentamethyl-diethylenetriamine, N, N-dimethylcyclohexylamine, triethylene diamine and triethylamine (mass ratio of pentamethyl-diethylenetriamine, N, N-dimethylcyclohexylamine, triethylene diamine and triethylamine is 1:1:1:1);
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 30 DEG C of conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then stirring reaction under the nitrogen atmosphere protective condition being 50 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 10h, stop after continuing reaction 2h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, the mol ratio of hydroxyl is 2:1; Described polyisocyanates is tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer (mass ratio of tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer is 1:1:2:1:1), described catalyzer is three n-butylbenzoic acid tin, and described organosilicon is KH-570;
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C, in described performed polymer, drip water, under agitation emulsification is carried out to performed polymer, then vacuumize removal solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 20wt%.
The rate of weight loss of hydrophobic flame-retardant polyurethane coating under 212 DEG C and 239 DEG C of conditions prepared by embodiment 9 is about 5% and 10% respectively, the limiting oxygen index(LOI) utilizing LFY-606B type digital display oxygen index measurer to measure this hydrophobic flame-retardant polyurethane coating is 28, Vo rank can be reached according to its flame retardant properties index of UL94 standard test, the surface contact angle utilizing MCAT type contact angle instrument to measure this hydrophobic flame-retardant polyurethane coating is 93 °, water-intake rate is 1.4%, illustrates that this hydrophobic flame-retardant polyurethane coating has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 10
The present embodiment is identical with embodiment 9, and its difference is: polymer polyatomic alcohol described in step one is less than four kinds in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG and polyethylene oxide; Described neutralizing agent is the one, two or three in pentamethyl-diethylenetriamine, N, N-dimethylcyclohexylamine, triethylene diamine and triethylamine;
Polyisocyanates described in step 3 is less than four kinds in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer.
Hydrophobic flame-retardant polyurethane coating prepared by the present embodiment has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 11
The present embodiment comprises the following steps:
Step one, take the various raw materials of following weight part: polyvalent alcohol 90 parts, fire retardant 40 parts, solvent 60 parts, hydrophilic chain extender 30 parts, neutralizing agent 50 parts, catalyzer 3 parts, organosilicon 30 parts; Described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 25%, and surplus is polymer polyatomic alcohol; Described biomass-based polyvalent alcohol is hydroxyethyl cyclodextrin; Described polymer polyatomic alcohol is polycaprolactone; Described solvent is acetone, described hydrophilic chain extender dihydroxyl half ester, and described fire retardant is tetrabromo-benzene anhydride diol, and described neutralizing agent is triethylene diamine;
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 60 DEG C of conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then stirring reaction under the nitrogen atmosphere protective condition being 80 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 9h, stop after continuing reaction 2h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, the mol ratio of hydroxyl is 1.5:1; Described polyisocyanates is diphenylmethanediisocyanate, and described catalyzer is stannous octoate, and described organosilicon is KH-550;
Step 4, treat that the temperature of performed polymer described in step 3 is down to 5 DEG C, in described performed polymer, drip water, under agitation emulsification is carried out to performed polymer, then vacuumize removal solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 55%.
The rate of weight loss of hydrophobic flame-retardant polyurethane coating under 260 DEG C and 281 DEG C of conditions prepared by embodiment 11 is about 5% and 10% respectively, the limiting oxygen index(LOI) utilizing LFY-606B type digital display oxygen index measurer to measure this hydrophobic flame-retardant polyurethane coating is 29, Vo rank can be reached according to its flame retardant properties index of UL94 standard test, the surface contact angle utilizing MCAT type contact angle instrument to measure this hydrophobic flame-retardant polyurethane coating is 101 °, water-intake rate is 0.9%, illustrates that this hydrophobic flame-retardant polyurethane coating has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 12
The present embodiment is identical with embodiment 11, its difference is: polymer polyatomic alcohol described in step one is polybutylene terephthalate, polyethylene terephthalate or poly-hexanodioic acid-1,4-butanediol ester, or be at least two kinds in polycaprolactone, polybutylene terephthalate, polyethylene terephthalate and poly-hexanodioic acid-BDO ester.
Hydrophobic flame-retardant polyurethane coating prepared by the present embodiment has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 13
The present embodiment comprises the following steps:
Step one, take the various raw materials of following weight part: polyvalent alcohol 80 parts, fire retardant 30 parts, solvent 50 parts, hydrophilic chain extender 20 parts, neutralizing agent 40 parts, catalyzer 2.5 parts, organosilicon 25 parts; Described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 20%, and surplus is polymer polyatomic alcohol; Described biomass-based polyvalent alcohol is hydroxypropyl cyclodextrin; Described polymer polyatomic alcohol is polycaprolactone and polybutylene terephthalate (mass ratio of polycaprolactone and polybutylene terephthalate is 1:2); Described solvent is acetone, and described hydrophilic chain extender is diaminobenzoic acid, and described fire retardant is dibromoneopentyl glycol, and described neutralizing agent is triethylamine;
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 40 DEG C of conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then stirring reaction under the nitrogen atmosphere protective condition being 70 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 8h, stop after continuing reaction 2h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, the mol ratio of hydroxyl is 2:1; Described polyisocyanates is hexamethylene diisocyanate, and described catalyzer is stannous octoate, and described organosilicon is KH-560;
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C, in described performed polymer, drip water, under agitation emulsification is carried out to performed polymer, then vacuumize removal solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 40wt%.
The rate of weight loss of hydrophobic flame-retardant polyurethane coating under 255 DEG C and 274 DEG C of conditions prepared by embodiment 13 is about 5% and 10% respectively, the limiting oxygen index(LOI) utilizing LFY-606B type digital display oxygen index measurer to measure this hydrophobic flame-retardant polyurethane coating is 30, Vo rank can be reached according to its flame retardant properties index of UL94 standard test, the surface contact angle utilizing MCAT type contact angle instrument to measure this hydrophobic flame-retardant polyurethane coating is 97 °, water-intake rate is 1.3%, illustrates that this hydrophobic flame-retardant polyurethane coating has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 14
The present embodiment is identical with embodiment 13, its difference is: polymer polyatomic alcohol described in step one is polybutylene terephthalate, polyethylene terephthalate or poly-hexanodioic acid-1, 4-butanediol ester, or be polycaprolactone, polybutylene terephthalate, polyethylene terephthalate and poly-hexanodioic acid-1, one in 4-butanediol ester or more than three kinds, or be polycaprolactone, polyethylene terephthalate and poly-hexanodioic acid-1, two kinds in 4-butanediol ester, or be polyethylene terephthalate and poly-hexanodioic acid-1, the mixture of a kind of and polybutylene terephthalate in 4-butanediol ester.
Hydrophobic flame-retardant polyurethane coating prepared by the present embodiment has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 15
The present embodiment comprises the following steps:
Step one, take the various raw materials of following weight part: polyvalent alcohol 30 parts, fire retardant 10 parts, solvent 30 parts, hydrophilic chain extender 5 parts, neutralizing agent 10 parts, catalyzer 1 part, organosilicon 5 parts; Described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 15.6%, and surplus is polymer polyatomic alcohol; Described biomass-based polyvalent alcohol is hydroxypropyl cyclodextrin; Described polymer polyatomic alcohol is polycaprolactone, polybutylene terephthalate and polyethylene terephthalate (mass ratio of polycaprolactone, polybutylene terephthalate and polyethylene terephthalate is 1:1:1); Described solvent is acetone, and described hydrophilic chain extender is diaminobenzoic acid, and described fire retardant is dibromoneopentyl glycol, and described neutralizing agent is triethylamine;
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 30 DEG C of conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then stirring reaction under the nitrogen atmosphere protective condition being 60 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 6h, stop after continuing reaction 1h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, the mol ratio of hydroxyl is 1.3:1; Described polyisocyanates is isophorone diisocyanate, and described catalyzer is dibutyl tin laurate, and described organosilicon is KH-560;
Step 4, treat that the temperature of performed polymer described in step 3 is down to 3 DEG C, in described performed polymer, drip water, under agitation emulsification is carried out to performed polymer, then vacuumize removal solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 25wt%.
The rate of weight loss of hydrophobic flame-retardant polyurethane coating under 232 DEG C and 260 DEG C of conditions prepared by embodiment 15 is about 5% and 10% respectively, the limiting oxygen index(LOI) utilizing LFY-606B type digital display oxygen index measurer to measure this hydrophobic flame-retardant polyurethane coating is 29, Vo rank can be reached according to its flame retardant properties index of UL94 standard test, the surface contact angle utilizing MCAT type contact angle instrument to measure this hydrophobic flame-retardant polyurethane coating is 92 °, water-intake rate is 1.6%, illustrates that this hydrophobic flame-retardant polyurethane coating has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 16
The present embodiment is identical with embodiment 15, its difference is: polymer polyatomic alcohol described in step one is polybutylene terephthalate, polyethylene terephthalate or poly-hexanodioic acid-1,4-butanediol ester, or be polycaprolactone, polybutylene terephthalate, polyethylene terephthalate and poly-hexanodioic acid-1, one in 4-butanediol ester, two kinds or four kinds, or be two kinds in polycaprolactone, polybutylene terephthalate and polyethylene terephthalate with the mixture of poly-hexanodioic acid-BDO ester.
Hydrophobic flame-retardant polyurethane coating prepared by the present embodiment has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 17
The present embodiment comprises the following steps:
Step one, take the various raw materials of following weight part: polyvalent alcohol 55 parts, fire retardant 24 parts, solvent 40 parts, hydrophilic chain extender 18 parts, neutralizing agent 28 parts, catalyzer 0.08 part, organosilicon 15 parts; Described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 22%, and surplus is polymer polyatomic alcohol; Described biomass-based polyvalent alcohol is hydroxypropyl cyclodextrin; Described polymer polyatomic alcohol is polycaprolactone, polybutylene terephthalate, polyethylene terephthalate and poly-hexanodioic acid-1,4-butanediol ester (mass ratio of polycaprolactone, polybutylene terephthalate, polyethylene terephthalate and poly-hexanodioic acid-BDO ester is 1:2:1:2); Described solvent is acetone, and described hydrophilic chain extender is dimethylol propionic acid, and described fire retardant is (two (2-hydroxyethyl) the aminomethy-lenephosphonic acids diethyl ester of N, N-), and described neutralizing agent is N, N-dimethylcyclohexylamine;
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 45 DEG C of conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then stirring reaction under the nitrogen atmosphere protective condition being 70 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 6h, stop after continuing reaction 2h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, the mol ratio of hydroxyl is 1.6:1; Described polyisocyanates is diphenylmethanediisocyanate, and described catalyzer is dibutyl tin laurate, and described organosilicon is KH-550;
Step 4, treat that the temperature of performed polymer described in step 3 is down to 0 DEG C, in described performed polymer, drip water, under agitation emulsification is carried out to performed polymer, then vacuumize removal solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 30wt%.
The rate of weight loss of hydrophobic flame-retardant polyurethane coating under 243 DEG C and 276 DEG C of conditions prepared by embodiment 17 is about 5% and 10% respectively, the limiting oxygen index(LOI) utilizing LFY-606B type digital display oxygen index measurer to measure this hydrophobic flame-retardant polyurethane coating is 28, Vo rank can be reached according to its flame retardant properties index of UL94 standard test, the surface contact angle utilizing MCAT type contact angle instrument to measure this hydrophobic flame-retardant polyurethane coating is 99 °, water-intake rate is 0.7%, illustrates that this hydrophobic flame-retardant polyurethane coating has good thermotolerance, flame retardant resistance and hydrophobicity.
Embodiment 18
The present embodiment is identical with embodiment 17, and its difference is: polymer polyatomic alcohol described in step one is the one, two or three in polybutylene terephthalate, polyethylene terephthalate and poly-hexanodioic acid-BDO ester.
Hydrophobic flame-retardant polyurethane coating prepared by the present embodiment has good thermotolerance, flame retardant resistance and hydrophobicity.
The above; it is only preferred embodiment of the present invention; not the present invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. a preparation method for hydrophobic flame-retardant polyurethane coating, is characterized in that, comprise the following steps:
Step one, take the various raw materials of following weight part: polyhydric alcohol composition 20 ~ 90 parts, fire retardant 5 ~ 40 parts, solvent 20 ~ 60 parts, hydrophilic chain extender 5 ~ 30 parts, neutralizing agent 5 ~ 50 parts, catalyzer 0.05 ~ 3 part, organosilicon 5 ~ 30 parts; Described polyhydric alcohol composition is mixed by biomass-based polyvalent alcohol and polymer polyatomic alcohol, and in described polyhydric alcohol composition, the mass content of biomass-based polyvalent alcohol is 10% ~ 25%, and surplus is polymer polyatomic alcohol; Described biomass-based polyvalent alcohol is modified rosin or hydroxyalkylated cyclodextrins, and described polymer polyatomic alcohol is polyester polyol or polyether glycol, and described solvent is acetone;
Step 2, polyhydric alcohol composition described in step one, fire retardant, solvent, hydrophilic chain extender and neutralizing agent to be mixed under 30 DEG C ~ 60 DEG C conditions, obtain mixture;
Step 3, in mixture described in step 2, drip catalyzer described in polyisocyanates and step one, then be stirring reaction under the nitrogen atmosphere protective condition of 50 DEG C ~ 90 DEG C in temperature, in reaction system, organosilicon described in step one is added after question response carries out 4h ~ 10h, stop after continuing reaction 1h ~ 3h, obtain performed polymer; In polyhydric alcohol composition described in isocyanate group in described polyisocyanates and step one, 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, in described performed polymer, drip water, under agitation emulsification is carried out to described performed polymer, then vacuumize and remove described solvent, obtain hydrophobic flame-retardant polyurethane coating; The quality consumption of described water is make the solid content of described hydrophobic flame-retardant polyurethane coating be 20wt% ~ 55wt%.
2. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating according to claim 1, it is characterized in that, the various raw materials taken in step one are respectively: polyhydric alcohol composition 30 ~ 80 parts, fire retardant 10 ~ 30 parts, solvent 30 ~ 50 parts, hydrophilic chain extender 5 ~ 20 parts, neutralizing agent 10 ~ 40 parts, catalyzer 1 ~ 3 part, organosilicon 5 ~ 25 parts.
3., according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating according to claim 2, it is characterized in that, the various raw materials taken are respectively: polyvalent alcohol 80 parts, fire retardant 20 parts, solvent 40 parts, hydrophilic chain extender 5 parts, neutralizing agent 10 parts, catalyzer 3 parts, organosilicon 5 parts.
4. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating according to claim 1, it is characterized in that, hydrophilic chain extender described in step one is one or more in dimethylol propionic acid, dihydroxyl half ester and diaminobenzoic acid; Described neutralizing agent is one or more in pentamethyl-diethylenetriamine, N, N-dimethylcyclohexylamine, triethylene diamine and triethylamine.
5., according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating according to claim 1, it is characterized in that, hydrophilic chain extender described in step one is N methyldiethanol amine, and described neutralizing agent is acetic acid.
6. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating according to claim 1, it is characterized in that, modified rosin described in step one is through toxilic acid and glycol modified rosin, and described hydroxyalkylated cyclodextrins is hydroxypropyl cyclodextrin or hydroxyethyl cyclodextrin; Described fire retardant is one or more in (N, N-two (2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester), two (4-hydroxy phenyl) phenyl phosphine oxide, tetrabromo-benzene anhydride diol and dibromoneopentyl glycol.
7. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating according to claim 1, it is characterized in that, polyester polyol described in step one is one or more in polycaprolactone, polybutylene terephthalate, polyethylene terephthalate and poly-hexanodioic acid-BDO ester; Described polyether glycol is one or more in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol, PTMG and polyethylene oxide.
8. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating according to claim 1, it is characterized in that, polyisocyanates described in step 3 is one or more in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate and hexamethylene diisocyanate trimer.
9. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating according to claim 1, it is characterized in that, catalyzer described in step 3 is one or more in dibutyl tin laurate, stannous octoate and three n-butylbenzoic acid tin.
10. according to the preparation method of a kind of hydrophobic flame-retardant polyurethane coating according to claim 1, it is characterized in that, organosilicon described in step 3 is one or more in KH-550, KH-560 and KH-570.
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