Fire-retardant, light resistance and low VOC polyurethane coating preparation method
Technical field
The present invention relates to a kind of preparation method of polyurethane coating, more particularly to fire-retardant, light resistance applies with low VOC polyurethane
Preparation method for material.
Background technology
Polyurethane is mainly used in the fields such as leather finish, textile printing and dyeing, paper-making industry, building coating and adhesive.By
In the coating and paint that are sprayed at external and internal wall, furniture or ironware surface, directly or indirectly contacted with the mankind, therefore have
Poison, harmful coating moment threaten the health of people.Further, since the field used often contacts sunshine, and in sunray
Pass through chemically containing the ultraviolet light being largely harmful to colored objects, its wavelength about 290~460nm, these harmful ultraviolet lights
Redox, make coating occur color change.
Polyurethane is polymerize makees catalyst frequently with dibutyl tin laurate, but because Heavy Metal, Sn is with polyurethane
Degraded and environment is damaged, how dibutyltindilaurate catalyzed remaining tin is fixed, reduce polyurethane
Coating residues have become a technical barrier to the extent of injury of environment.
In order to improve the light resistance of polyurethane resin, frequently with the mode for adding ultra-violet absorber and antioxidant, but
It is larger that traditional synthetized oxidation preventive agent has butylhydroxy anisole, t-butyl hydroperoxide and TBHQ etc. to have
Toxic side effect and carcinogenicity, and with it is traditional add organosilicon material improve water proofing property effect it is unsatisfactory, therefore
Need to find the more waterproof of high-efficiency environment friendly and fast light measure.
Aqueous polyurethane(Also known as water-based polyurethane)It is a kind of poly- containing hydrophilic radical in the strand of polyurethane
Urethane resin, there is very strong compatibility with water, can be allowed to disperse and formed stable system in water using specific technique.
Aqueous polyurethane is mainly used in leather finish, textile printing and dyeing, paper-making industry, building coating, adhesive and steel moulder's paint etc.,
Involved is nearly all combustible material, and these materials necessarily turn into the peace for triggering fire when in use as not fire retardant treated
Full hidden danger.Aqueous polyurethane it is flame-retarded, be one of important directions of aqueous polyurethane functionalization.
Polyurethane coating, i.e. carbamate coating, it, which is applied in membrane molecule, contains a considerable amount of polyurethane ester bonds.
Polyurethane coating, also containing urea bond, ehter bond, ester bond, allophanic acid ester bond, is a kind of function admirable, answered in addition to containing ammonia ester bond
With extensive coating
VOC (Volatile Organic Compounds) refers to volatilizable in solvent based coating and human contact or suction
The solvent of disease can be caused after entering.Often contain VOC in polyurethane coating.Health hazards of the VOC to human body is very big, and it is not only right
Skin has corrosion function, and has stimulation and destruction to human central nervous system, blood forming organ, respiratory system, can
Cause the symptom such as headache, nausea, uncomfortable in chest, weak, vomiting, can be twitched when serious, even death of going into a coma.The whole world is every year because use has
Poison learn solvent based coating and caused by the economic loss brought of environmental disruption and human injury be up to tens billion of dollars.Therefore,
Generation
Main coating material production state has launched respectively limitation VOC exhaust emission regulation in boundary.Such as in the world, press
According to European Community's ecological mark product --- the regulation of relevant VOC limitations, the most commonly used a kind of coating of people's house decoration are
30 g/L, the coating state compulsory standard in China《Limits of harmful substances in indoor decorating and refurnishing materials interior wall coating》Regulation
VOC must not exceed 200 g/L.Therefore, the direction that low VOC polyurethane coatings are polyurethane coating development is developed.
The content of the invention
The technical problem to be solved by the invention is to provide fire-retardant, light resistance and low VOC polyurethane coating preparation side
Method, and effectively fixed its toxicity of mitigation is carried out by selecting catalyst and improves polymerization yield rate, reduce VOC content.
Technical scheme is as follows:
1. fire-retardant, light resistance and low VOC polyurethane coating preparation method, it is characterised in that:
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
9g, boric acid 23g, diethanol amine 20g, hexaphenoxycyclotriphosphazene 6.2g and 3- aminopropyl ortho-siliformic acid 2.6g and water 60g,
PH to 4 is adjusted, is heated to 70 DEG C, stirring reaction 1h, EDTAP dipotassium ethylene diamine tetraacetate 2g is added, 60 DEG C of stirring reaction 2h, is changed
Property manganese hypophosphite;
(2), with agitator, condenser pipe, thermometer 250ml there-necked flasks in add triethylene tetramine 0.22g, poly- four
Hydrogen furans ether glycol 70g and hexamethylene diisocyanate 15g, react 2h at 80 DEG C, obtain base polyurethane prepolymer for use as A, described
The molecular weight of PTMG is 1000;
(3), 0.62g acetamides and 8.2g MEKs are added into performed polymer A, 3.5h is reacted under the conditions of 75 DEG C, is added
2g steps(1)Modification manganese hypophosphite, 4g4- Carboxybenzeneboronic acids and the diethylene triamine pentamethylene phosphonic 2.5g of preparation, reaction temperature
80 DEG C, reaction time 2h, add 7.1g triethylamines and carry out neutralization reaction 60min, add vitamin C 0.9g, water 70g is stirred
Emulsification, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
2. fire-retardant, light resistance and low VOC polyurethane coating preparation method, it is characterised in that:
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
6g, boric acid 10g, diethanol amine 15g, melamine cyanurate 12g and 4- hydroxyphenethylamine 2.8g and water 40g, adjust pH
To 4,70 DEG C, stirring reaction 1h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 2g, 60 DEG C of stirring reaction 1h, obtains modified phosphorus
Sour manganese;
(2), with agitator, condenser pipe, thermometer 500ml there-necked flasks in add carbodiimides 0.64g, poly- four
Hydrogen furans ether glycol 65g and hexamethylene diisocyanate 40g, react 2h at 90 DEG C, obtain base polyurethane prepolymer for use as A, described
The molecular weight of PTMG is 2000;
(3), into performed polymer A add dithiothreitol (DTT) 3.2g and MEK 16.5g, react 2.5h under the conditions of 75 DEG C,
Add step(1)Modification manganese hypophosphite 6g, 4- Carboxybenzeneboronic acid 3.4g and ATMP 2.2g of preparation, reaction temperature
95 DEG C, reaction time 2h, add triethylamine 13.5g and carry out neutralization reaction 50min, add 4,8- dihydroxy quinoline -2- formic acid
2.7g, water 100g are stirred emulsification, obtain the polyurethane coating of fire-retardant, light resistance and low VOC.
3. fire-retardant, light resistance and low VOC polyurethane coating preparation method, it is characterised in that:
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
4.2g, boric acid 26g, diethanol amine 22g, hexamethylolmelamine 12g and 4,8- dihydroxy quinoline -2- formic acid 2.2g and water
45g, pH to 4 is adjusted, 70 DEG C, stirring reaction 1h is heated to, EDTAP dipotassium ethylene diamine tetraacetate 2g, 50 DEG C of stirring reaction 1h, is changed
Property manganese hypophosphite;
(2), with agitator, condenser pipe, thermometer 500ml there-necked flasks in, add sebacic dihydrazide 0.32g,
PTMG 85g and hexamethylene diisocyanate 32g, reacts 1h at 75 DEG C, obtains base polyurethane prepolymer for use as A,
The molecular weight of the PTMG is 1000;
(3), into performed polymer A add the equal three nitrogen borine 2.4g and MEK 20.4g of hexahydro, reacted under the conditions of 70 DEG C
2.0h, add step(1)Modification manganese hypophosphite 8.9g, 4- Carboxybenzeneboronic acid 3.8g and TAC of preparation
2.6g, 75 DEG C, reaction time 2.5h of reaction temperature, add triethylamine 15.2g and carry out neutralization reaction 30min, add sodium salicylate
2.2g, water 150g stirring are emulsified, and obtain the polyurethane coating of fire-retardant, light resistance and low VOC.
4. fire-retardant, light resistance and low VOC polyurethane coating preparation method, it is characterised in that:
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
6.2g, boric acid 13g, diethanol amine 22g, hexaphenoxycyclotriphosphazene 8.5g and 3- aminopropyl ortho-siliformic acid 3.5g and water
40g, pH to 4 is adjusted, be heated to 70 DEG C, stirring reaction 3h, added EDTAP dipotassium ethylene diamine tetraacetate 2g, 50 DEG C of stirring reaction 2h, obtain
To modified manganese hypophosphite;
(2), with agitator, condenser pipe, thermometer 250ml there-necked flasks in add tributyl 2-acetylcitrate
0.15g, PTMG 60g and hexamethylene diisocyanate 20g, react 2h at 80 DEG C, it is pre- to obtain polyurethane
Aggressiveness A, the molecular weight of the PTMG is 1000;
(3), into performed polymer A add acetamide 0.52g and MEK 9.2g, 2.5h is reacted under the conditions of 60 DEG C, add
4g steps(1)Modification manganese hypophosphite, 3.6g4- Carboxybenzeneboronic acids and the trimethylol-propane trimethacrylate 2.5g of preparation,
70 DEG C, reaction time 2h of reaction temperature, add 7.5g triethylamines and carry out neutralization reaction 40min, add vitamin C 1.6g, water 70g
Emulsification is stirred, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
5. fire-retardant, light resistance and low VOC polyurethane coating preparation method, it is characterised in that:
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
3g, boric acid 10g, diethanol amine 35g, melamine cyanurate 12g and 4,8- dihydroxy quinoline -2- formic acid 2.8g and water
70g, pH to 4 is adjusted, be heated to 70 DEG C, stirring reaction 2h, added EDTAP dipotassium ethylene diamine tetraacetate 2g, 50 DEG C of stirring reaction 2h, obtain
To modified manganese hypophosphite;
(2), with agitator, condenser pipe, thermometer 500ml there-necked flasks in add 5- Aminotetrazoles 0.84g, poly- four
Hydrogen furans ether glycol 80g and hexamethylene diisocyanate 40g, react 2h at 90 DEG C, obtain base polyurethane prepolymer for use as A, described
The molecular weight of PTMG is 2000;
(3), into performed polymer A add dithiothreitol (DTT) 3.9g and MEK 24.5g, react 2.5h under the conditions of 75 DEG C,
Add step(1)Modification manganese hypophosphite 8.9g, 4- Carboxybenzeneboronic acid 6.4g and cyanuric acid 3.8g of preparation, reaction temperature 85
DEG C, reaction time 2h, add triethylamine 14.5g and carry out neutralization reaction 60min, 4,8- dihydroxy quinoline -2- formic acid 3.7g, water
75g is stirred emulsification, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
Advantage of the invention is that:
(1)Triethylene tetramine, carbodiimides, sebacic dihydrazide, tributyl 2-acetylcitrate and 5- Aminotetrazoles replace
It is tin compound catalyst for traditional advantage;
(2)Diethylene triamine pentamethylene phosphonic, ATMP, TAC, trimethylolpropane
Trimethyl acrylic ester, cyanuric acid are crosslinked to polymer, improve the defects of traditional HDI polyurethane intensity is not high, together
When reactant is chelated, add absorption small molecule, reduce the VOC of release;
(3)The equal three nitrogen borine of acetamide, dithiothreitol (DTT), hexahydro is not only with chain extender but also with light resistance;
(4)Hexaphenoxycyclotriphosphazene, melamine cyanurate, hexamethylolmelamine have fire retardation,
3- aminopropyls ortho-siliformic acid, 4- hydroxyphenethylamines, 4,8- dihydroxy quinoline -2- formic acid improve its resistance to fire-retardant carry out synergy
Combustion property.
Embodiment
The present invention is further illustrated with reference to example.
Example one
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
9g, boric acid 23g, diethanol amine 20g, hexaphenoxycyclotriphosphazene 6.2g and 3- aminopropyl ortho-siliformic acid 2.6g and water 60g,
PH to 4 is adjusted, is heated to 70 DEG C, stirring reaction 1h, EDTAP dipotassium ethylene diamine tetraacetate 2g is added, 60 DEG C of stirring reaction 2h, is changed
Property manganese hypophosphite;
(2), with agitator, condenser pipe, thermometer 250ml there-necked flasks in add triethylene tetramine 0.22g, poly- four
Hydrogen furans ether glycol 70g and hexamethylene diisocyanate 15g, react 2h at 80 DEG C, obtain base polyurethane prepolymer for use as A, described
The molecular weight of PTMG is 1000;
(3), 0.62g acetamides and 8.2g MEKs are added into performed polymer A, 3.5h is reacted under the conditions of 75 DEG C, is added
2g steps(1)Modification manganese hypophosphite, 4g4- Carboxybenzeneboronic acids and the diethylene triamine pentamethylene phosphonic 2.5g of preparation, reaction temperature
80 DEG C, reaction time 2h, add 7.1g triethylamines and carry out neutralization reaction 60min, add vitamin C 0.9g, water 70g is stirred
Emulsification, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
Example two
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
6g, boric acid 10g, diethanol amine 15g, melamine cyanurate 12g and 4- hydroxyphenethylamine 2.8g and water 40g, adjust pH
To 4,70 DEG C, stirring reaction 1h are heated to, adds EDTAP dipotassium ethylene diamine tetraacetate 2g, 60 DEG C of stirring reaction 1h, obtains modified phosphorus
Sour manganese;
(2), with agitator, condenser pipe, thermometer 500ml there-necked flasks in add carbodiimides 0.64g, poly- four
Hydrogen furans ether glycol 65g and hexamethylene diisocyanate 40g, react 2h at 90 DEG C, obtain base polyurethane prepolymer for use as A, described
The molecular weight of PTMG is 2000;
(3), into performed polymer A add dithiothreitol (DTT) 3.2g and MEK 16.5g, react 2.5h under the conditions of 75 DEG C,
Add step(1)Modification manganese hypophosphite 6g, 4- Carboxybenzeneboronic acid 3.4g and ATMP 2.2g of preparation, reaction temperature
95 DEG C, reaction time 2h, add triethylamine 13.5g and carry out neutralization reaction 50min, add 4,8- dihydroxy quinoline -2- formic acid
2.7g, water 100g are stirred emulsification, obtain the polyurethane coating of fire-retardant, light resistance and low VOC.
Example three
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
4.2g, boric acid 26g, diethanol amine 22g, hexamethylolmelamine 12g and 4,8- dihydroxy quinoline -2- formic acid 2.2g and water
45g, pH to 4 is adjusted, 70 DEG C, stirring reaction 1h is heated to, EDTAP dipotassium ethylene diamine tetraacetate 2g, 50 DEG C of stirring reaction 1h, is changed
Property manganese hypophosphite;
(2), with agitator, condenser pipe, thermometer 500ml there-necked flasks in, add sebacic dihydrazide 0.32g,
PTMG 85g and hexamethylene diisocyanate 32g, reacts 1h at 75 DEG C, obtains base polyurethane prepolymer for use as A,
The molecular weight of the PTMG is 1000;
(3), into performed polymer A add the equal three nitrogen borine 2.4g and MEK 20.4g of hexahydro, reacted under the conditions of 70 DEG C
2.0h, add step(1)Modification manganese hypophosphite 8.9g, 4- Carboxybenzeneboronic acid 3.8g and TAC of preparation
2.6g, 75 DEG C, reaction time 2.5h of reaction temperature, add triethylamine 15.2g and carry out neutralization reaction 30min, add sodium salicylate
2.2g, water 150g stirring are emulsified, and obtain the polyurethane coating of fire-retardant, light resistance and low VOC.
Example four
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
6.2g, boric acid 13g, diethanol amine 22g, hexaphenoxycyclotriphosphazene 8.5g and 3- aminopropyl ortho-siliformic acid 3.5g and water
40g, pH to 4 is adjusted, be heated to 70 DEG C, stirring reaction 3h, added EDTAP dipotassium ethylene diamine tetraacetate 2g, 50 DEG C of stirring reaction 2h, obtain
To modified manganese hypophosphite;
(2), with agitator, condenser pipe, thermometer 250ml there-necked flasks in add tributyl 2-acetylcitrate
0.15g, PTMG 60g and hexamethylene diisocyanate 20g, react 2h at 80 DEG C, it is pre- to obtain polyurethane
Aggressiveness A, the molecular weight of the PTMG is 1000;
(3), into performed polymer A add acetamide 0.52g and MEK 9.2g, 2.5h is reacted under the conditions of 60 DEG C, add
4g steps(1)Modification manganese hypophosphite, 3.6g4- Carboxybenzeneboronic acids and the trimethylol-propane trimethacrylate 2.5g of preparation,
70 DEG C, reaction time 2h of reaction temperature, add 7.5g triethylamines and carry out neutralization reaction 40min, add vitamin C 1.6g, water 70g
Emulsification is stirred, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
Example five
(1), modified manganese hypophosphite preparation:With agitator, thermometer 250ml there-necked flasks in add manganese hypophosphite
3g, boric acid 10g, diethanol amine 35g, melamine cyanurate 12g and 4,8- dihydroxy quinoline -2- formic acid 2.8g and water
70g, pH to 4 is adjusted, be heated to 70 DEG C, stirring reaction 2h, added EDTAP dipotassium ethylene diamine tetraacetate 2g, 50 DEG C of stirring reaction 2h, obtain
To modified manganese hypophosphite;
(2), with agitator, condenser pipe, thermometer 500ml there-necked flasks in add 5- Aminotetrazoles 0.84g, poly- four
Hydrogen furans ether glycol 80g and hexamethylene diisocyanate 40g, react 2h at 90 DEG C, obtain base polyurethane prepolymer for use as A, described
The molecular weight of PTMG is 2000;
(3), into performed polymer A add dithiothreitol (DTT) 3.9g and MEK 24.5g, react 2.5h under the conditions of 75 DEG C,
Add step(1)Modification manganese hypophosphite 8.9g, 4- Carboxybenzeneboronic acid 6.4g and cyanuric acid 3.8g of preparation, reaction temperature 85
DEG C, reaction time 2h, add triethylamine 14.5g and carry out neutralization reaction 60min, 4,8- dihydroxy quinoline -2- formic acid 3.7g, water
75g is stirred emulsification, obtains the polyurethane coating of fire-retardant, light resistance and low VOC.
Beneficial effects of the present invention are further illustrated below by relevant experimental data:PU-1 is to be selected from Wuxi City great waves
The polyurethane antiseptic finishing paint of Chemical Co., Ltd..
Table one is fire-retardant, light resistance and low VOC polyurethane coating institute filming performance
Experimental group |
Example one |
Example two |
Example three |
Example four |
Example five |
PU-1 |
Hardness |
B |
B |
B |
B |
B |
B |
Adhesive force/level |
3 |
2 |
3 |
3 |
2 |
2 |
Pliability/mm |
3 |
3 |
3 |
2 |
3 |
2 |
From table two it can be found that from film outward appearance, hardness, adhesive force, flexibility better performances.
Table two is fire-retardant, the mechanical property of film obtained by light resistance and low VOC polyurethane coating
Experimental group |
Example one |
Example two |
Example three |
Example four |
Example five |
PU-1 |
Elongation at break/% |
162 |
158 |
161 |
167 |
172 |
157 |
Tensile strength/MPa |
5.9 |
5.6 |
5.2 |
7.4 |
8.8 |
5.4 |
Abrasion resisting/level |
3.0 |
4 |
4.0 |
3.5 |
4.5 |
3 |
The middle finger object detection method of table two refers to(Auspicious leather finish physical and chemical inspection [M] the China Light Industry Press of Jiang Wei,
1999), film elongation at break, tensile strength, wear-resistant performance are preferable obtained by coating of the present invention.
Anti-flammability is to pass through smoke density method(Maximum smoke density, reach the maximum smoke density time), oxygen index (OI), vertical combustion refer to
Mark(Flaming combustion time, glowing time)To weigh, elongation at break characterizes its mechanical property.
Table three is fire-retardant, the anti-flammability of film obtained by light resistance and low VOC polyurethane coating
|
Example one |
Example two |
Example three |
Example four |
Example five |
PU-1 |
Maximum smoke density |
12 |
26 |
32 |
16 |
11 |
59 |
Reach maximum smoke density time/s |
180 |
180 |
195 |
225 |
185 |
150 |
Oxygen index (OI) |
27.6 |
26.8 |
24.9 |
26.8 |
27.2 |
24.1 |
Flaming combustion time/s |
12.5 |
15.8 |
10.6 |
9.9 |
7.2 |
24 |
Glowing time/s |
0.1 |
0.2 |
0 |
0 |
0 |
1 |
The detection of the indices of table three is respectively according to following standard:Smoke density determines according to GB8323-2008, oxygen index (OI)
Using GB/T5454-1997《Textile combustion performance test-oxygen index method》Measure;Flaming combustion time and glowing time
It is by GB/T 5455-1997《Textile combustion can test-normal beam technique》To determine.
As shown in Table 3, when the present invention is burnt with sunproof polyurethane coating with adhesive gained film, maximum smoke density shows
Writing reduces, and reaches the maximum smoke density time and significantly extends, oxygen index (OI) significantly improves, and burning time substantially shortens.
For quantitative description resistance to light of coating energy, detected using spectrophotometer, to obtain inverse difference △ E,
To describe the light resistance of coating and finish paint.△ E represent color change degree, and △ E are bigger, and color change is more obvious.It is general next
Say, △ E values are 0~1.5 category slight change;△ E values are that 1.5~3.0 category can feel change;△ E values, which are that 3.0~6.0 category are obvious, to be become
Change(Referring to Wang Fang, party's climax, Wang Liqin, light degradation [J] the Northwest Universitys journal of several organic historical relic's protection polymer coatings,
2005,35(5):56~58).
Table four is fire-retardant, the light resistance of film obtained by light resistance and low VOC polyurethane coating
Time/min |
Example one |
Example two |
Example three |
Example four |
Example five |
PU-1 |
90 |
0.1 |
0.2 |
0.3 |
0.2 |
0.1 |
0.2 |
150 |
0.3 |
0.3 |
0.4 |
0.5 |
0.2 |
0.3 |
270 |
0.5 |
0.4 |
0.4 |
0.5 |
0.4 |
0.6 |
330 |
0.7 |
0.8 |
0.5 |
0.5 |
0.4 |
0.9 |
390 |
0.8 |
0.8 |
0.7 |
0.7 |
0.5 |
1.0 |
450 |
0.9 |
0.8 |
0.7 |
0.7 |
0.6 |
1.2 |
510 |
1.0 |
1.1 |
0.9 |
0.9 |
0.6 |
1.9 |
540 |
1.1 |
1.2 |
1.1 |
0.9 |
0.8 |
2.2 |
600 |
1.3 |
1.2 |
1.2 |
1.2 |
0.8 |
2.8 |
From table four it can be found that the coating light resistance prepared by example one to example five is in the range of slight change, show
Show good light resistance, and PU-1 already belongs to that change can be felt in 510min
Tested according to limits of harmful substances standard in GB24408-2009 exterior coatings:
Table five is fire-retardant, light resistance and low VOC polyurethane coating VOC
|
Example one |
Example two |
Example three |
Example four |
Example five |
PU-1 |
VOC (VOC) content |
106 |
112 |
134 |
146 |
137 |
215 |