CN108384429A - A kind of polyurethane coating - Google Patents
A kind of polyurethane coating Download PDFInfo
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- CN108384429A CN108384429A CN201810225516.4A CN201810225516A CN108384429A CN 108384429 A CN108384429 A CN 108384429A CN 201810225516 A CN201810225516 A CN 201810225516A CN 108384429 A CN108384429 A CN 108384429A
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- polyurethane coating
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Abstract
The invention discloses polyurethane coatings, trimethyl silanol 3.5g and methyl ethyl ketone 16.8g is added into performed polymer A, 3.5h is reacted under the conditions of 75 DEG C, modification manganese hypophosphite 7.2g prepared by step (1) is added, 4 Carboxybenzeneboronic acid 3.6g and nitrilotriacetic acid 2.8g, 85 DEG C of reaction temperature, reaction time 1h, triethylamine 14.5g is added and carries out neutralization reaction 60min, it is added 4, 8 dihydroxy quinoline, 2 formic acid 2.8g, water 110g is stirred emulsification 1h, it obtains fire-retardant, the polyurethane coating of waterproof and low VOC, prepared is fire-retardant, the polyurethane coating environmental protection of waterproof and low VOC, it is cheap, it is widely used in wall, furniture, ironware surface, as plastics, glass, papermaking, the adhesive of weaving.
Description
The application is application No. is 2016107611630, and the applying date is on 08 30th, 2016, and invention and created name is
The divisional application of the patent of " the polyurethane coating preparation method of fire-retardant, waterproof and low VOC ".
Technical field
The present invention relates to a kind of preparation method of polyurethane coating, more particularly to fire-retardant, waterproof and low VOC polyurethane coatings
Preparation method.
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 people's health.In addition, due to the use of field often contact sunlight, and in sunray
Containing largely to the harmful ultraviolet light of colored objects, wavelength about 290~460nm, these harmful ultraviolet lights pass through chemically
Redox, make coating occur color variation.
Polyurethane is polymerize makees catalyst frequently with dibutyl tin laurate, but since Heavy Metal, Sn is with polyurethane
Degradation and cause damages to environment, how the tin of dibutyltindilaurate catalyzed remnants is fixed, reduce polyurethane
Coating residues have become a technical barrier to the extent of injury of environment.
Aqueous polyurethane (also known as water-based polyurethane) is a kind of poly- containing hydrophilic radical in the strand of polyurethane
Urethane resin is had 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, these materials necessarily become the peace for causing fire when in use as not fire retardant treated
Full hidden danger.Aqueous polyurethane it is flame-retarded, be one of important directions of functionalization of waterborne polyurethane.
Polyurethane coating, i.e. carbamate coating apply and contain a considerable amount of polyurethane ester bonds in membrane molecule.
Polyurethane coating also contains urea bond, ehter bond, ester bond, allophanic acid ester bond in addition to containing ammonia ester bond, is a kind of function admirable, answers
With extensive coating.
VOC (Volatile Organic Compounds) refers to volatilizable in solvent based coating and human contact or suction
It can lead to the solvent of disease after entering.Often contain VOC in polyurethane coating.VOC is very big to the health hazard of human body, it is not only to skin
Skin has corrosion function, and has stimulation and destruction to human central nervous system, blood forming organ, respiratory system, can draw
The symptoms such as headache, nausea, uncomfortable in chest, weak, vomiting are played, can be twitched when serious, even death of going into a coma.The whole world is toxic because using every year
Chemical solution dosage form 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 the exhaust emission regulation of limitation VOC in boundary.Such as in the world, it is given birth to according to the European Community
State famous special product --- the regulation of related VOC limitations, the most commonly used a kind of coating of people's house decoration is 30g/L, China
Coating state compulsory standard《Limits of harmful substances in indoor decorating and refurnishing materials interior wall coating》Regulation VOC must not exceed
200g/L.Therefore, develop the direction that low VOC polyurethane coatings are polyurethane coating development.
Invention content
The technical problem to be solved by the invention is to provide the polyurethane coating preparation method of fire-retardant, waterproof and low VOC,
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. the polyurethane coating preparation method of fire-retardant, waterproof and low VOC, it is characterised in that：
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
11.2g, boric acid 25.6g, diethanol amine 28g, hexaphenoxycyclotriphosphazene 7.2g and phloridzin 2.8g and water 65g adjust pH
To 4,80 DEG C are heated to, is stirred to react 2h, EDTAP dipotassium ethylene diamine tetraacetate 1.6g is added, 70 DEG C are stirred to react 1h, obtain modified time
Manganese phosphate；
(2), with blender, condenser pipe, thermometer 250ml there-necked flasks in be added azoformic acid dibenzyl ester
0.25g, polytetrahydrofuran ether glycol 72g and hexamethylene diisocyanate 18g, react 1h at 70 DEG C, it is pre- to obtain polyurethane
The molecular weight of aggressiveness A, the polytetrahydrofuran ether glycol are 500；
(3), the equal three nitrogen borine of 0.68g hexahydros and 8.8g methyl ethyl ketone are added into performed polymer A, is reacted under the conditions of 70 DEG C
Modification manganese hypophosphite, 3.2g4- Carboxybenzeneboronic acids and N- hydroxy thiosuccinimides prepared by 1g steps (1) is added in 3.0h
3.5g, 70 DEG C, reaction time 1h of reaction temperature are added 7.8g triethylamines and carry out neutralization reaction 70min, and water 70g is stirred breast
Change 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
2. the polyurethane coating preparation method of fire-retardant, waterproof and low VOC, it is characterised in that：
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
5.2g, boric acid 8g, diethanol amine 18g, benzilic acid 14g and 4- hydroxyphenethylamine 2.9g and water 70g adjust pH to 4,
60 DEG C are heated to, 2h is stirred to react, EDTAP dipotassium ethylene diamine tetraacetate 1.6g is added, 70 DEG C are stirred to react 2h, obtain modified hypophosphorous acid
Manganese；
(2), with blender, condenser pipe, thermometer 500ml there-necked flasks in be added；Tetramethyl ammonium chloride 0.74g,
Polytetrahydrofuran ether glycol 70g and hexamethylene diisocyanate 30g, reacts 4h at 80 DEG C, obtains base polyurethane prepolymer for use as A,
The molecular weight of the polytetrahydrofuran ether glycol is 1000；
(3), trimethyl silanol 3.5g and methyl ethyl ketone 16.8g is added into performed polymer A, reacts 3.5h under the conditions of 75 DEG C,
Modification manganese hypophosphite 7.2g, 4- Carboxybenzeneboronic acid 3.6g and nitrilotriacetic acid 2.8g prepared by step (1), reaction temperature 85 is added
DEG C, reaction time 1h, addition triethylamine 14.5g progress neutralization reaction 60min, addition 4,8- dihydroxy quinoline -2- formic acid 2.8g,
Water 110g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
3. the polyurethane coating preparation method of fire-retardant, light resistance and low VOC, it is characterised in that：
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
8.2g, boric acid 26.4g, diethanol amine 22.6g, hexamethylolmelamine 13g and benzilic acid 2.8g and water 55g,
PH to 4 is adjusted, 80 DEG C is heated to, is stirred to react 1h, EDTAP dipotassium ethylene diamine tetraacetate 0.9g, 60 DEG C are stirred to react 2h, are modified
Manganese hypophosphite；
(2), with blender, condenser pipe, thermometer 500ml there-necked flasks in, be added stearyl trimethyl ammonium chloride
0.52g, polytetrahydrofuran ether glycol 80g and hexamethylene diisocyanate 36g, react 2h at 70 DEG C, it is pre- to obtain polyurethane
The molecular weight of aggressiveness A, the polytetrahydrofuran ether glycol are 1000；
(3), nitrilotriacetic acid 2.6g and methyl ethyl ketone 21.4g is added into performed polymer A, reacts 2.5h under the conditions of 80 DEG C, adds
Enter modification manganese hypophosphite 7.9g, 4- Carboxybenzeneboronic acid 4.8g and diphenyl methane dimaleimide 3.6g of step (1) preparation, instead
85 DEG C, reaction time 3.5h of temperature is answered, triethylamine 16.2g is added and carries out neutralization reaction 40min, sodium salicylate 3.2g, water is added
160g stirrings carry out emulsification 1h, obtain the polyurethane coating of fire-retardant, waterproof and low VOC.
4. the polyurethane coating preparation method of fire-retardant, waterproof and low VOC, it is characterised in that：
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
6.4g, boric acid 14g, diethanol amine 23.2g, hexaphenoxycyclotriphosphazene 9.5g and phloridzin 5.5g and water 80g adjust pH and arrive
4,80 DEG C are heated to, 2h is stirred to react, EDTAP dipotassium ethylene diamine tetraacetate 1.5g is added, 50 DEG C are stirred to react 3h, obtain modified phosphorus
Sour manganese；
(2), with blender, condenser pipe, thermometer 250ml there-necked flasks in triethyl aluminum 0.35g, poly- tetrahydrochysene is added
Furans ether glycol 60g and hexamethylene diisocyanate 20g, react 2h at 80 DEG C, obtain base polyurethane prepolymer for use as A, described poly-
The molecular weight of tetrahydrofuran ether glycol is 1000；
(3), nitrilotriacetic acid 0.52g and methyl ethyl ketone 9.2g is added into performed polymer A, reacts 3.5h under the conditions of 70 DEG C, adds
Enter modification manganese hypophosphite, 3.6g4- Carboxybenzeneboronic acids and the semicarbazides 2.6g of 4g steps (1) preparation, 80 DEG C of reaction temperature, reaction
Time 1h is added 7.5g triethylamines and carries out neutralization reaction 30min, and water 70g is added and is stirred emulsification 1h, obtains fire-retardant, waterproof
With the polyurethane coating of low VOC.
5. the polyurethane coating preparation method of fire-retardant, waterproof and low VOC, it is characterised in that：
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
3.2g, boric acid 9g, diethanol amine 36g, melamine cyanurate 15g and benzilic acid 3.2g and water 80g adjust pH
To 4,70 DEG C are heated to, is stirred to react 2h, EDTAP dipotassium ethylene diamine tetraacetate 1.8g is added, 70 DEG C are stirred to react 2h, obtain modified time
Manganese phosphate；
(2), with blender, condenser pipe, thermometer 500ml there-necked flasks in isopropylmagnesium chloride 0.94g, poly- is added
Tetrahydrofuran ether glycol 100g and hexamethylene diisocyanate 50g, react 1h at 90 DEG C, obtain base polyurethane prepolymer for use as A, institute
The molecular weight for stating polytetrahydrofuran ether glycol is 2000；
(3), trimethyl silanol 4.2g and methyl ethyl ketone 25.5g is added into performed polymer A, reacts 3.5h under the conditions of 75 DEG C,
Modification manganese hypophosphite 9.9g, 4- Carboxybenzeneboronic acid 7.4g and tetraethylenepentamine 2.8g prepared by step (1), reaction temperature 95 is added
DEG C, reaction time 1h, addition triethylamine 15.5g progress neutralization reaction 60min, addition 4,8- dihydroxy quinoline -2- formic acid 3.7g,
Water 75g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
Advantage of the invention is that：
(1) azoformic acid dibenzyl ester, tetramethyl ammonium chloride, stearyl trimethyl ammonium chloride, triethyl aluminum and isopropyl
Magnesium chloride substitutes traditional advantage and is tin compound catalyst；
(2) N- hydroxy thiosuccinimides, nitrilotriacetic acid, diphenyl methane dimaleimide, semicarbazides, four ethylene five
Amine is crosslinked polymer, improves the not high defect of traditional HDI polyurethane intensity, while chelating to reactant, increases
Add absorption small molecule, reduces the VOC of release；
(3) the equal three nitrogen borine of hexahydro, trimethyl silanol, nitrilotriacetic acid are not only with chain extender but also with light resistance；
(4) hexaphenoxycyclotriphosphazene, melamine cyanurate, hexamethylolmelamine have fire retardation, root
Skin glucoside, benzilic acid improve its anti-flammability to fire-retardant carry out synergy.
Specific implementation mode
It is further illustrated the present invention with reference to example.
Example one
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
11.2g, boric acid 25.6g, diethanol amine 28g, hexaphenoxycyclotriphosphazene 7.2g and phloridzin 2.8g and water 65g adjust pH
To 4,80 DEG C are heated to, is stirred to react 2h, EDTAP dipotassium ethylene diamine tetraacetate 1.6g is added, 70 DEG C are stirred to react 1h, obtain modified time
Manganese phosphate；
(2), with blender, condenser pipe, thermometer 250ml there-necked flasks in be added azoformic acid dibenzyl ester
0.25g, polytetrahydrofuran ether glycol 72g and hexamethylene diisocyanate 18g, react 1h at 70 DEG C, it is pre- to obtain polyurethane
The molecular weight of aggressiveness A, the polytetrahydrofuran ether glycol are 500；
(3), the equal three nitrogen borine of 0.68g hexahydros and 8.8g methyl ethyl ketone are added into performed polymer A, is reacted under the conditions of 70 DEG C
Modification manganese hypophosphite, 3.2g4- Carboxybenzeneboronic acids and N- hydroxy thiosuccinimides prepared by 1g steps (1) is added in 3.0h
3.5g, 70 DEG C, reaction time 1h of reaction temperature are added 7.8g triethylamines and carry out neutralization reaction 70min, and water 70g is stirred breast
Change 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
Example two
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
5.2g, boric acid 8g, diethanol amine 18g, benzilic acid 14g and 4- hydroxyphenethylamine 2.9g and water 70g adjust pH to 4,
60 DEG C are heated to, 2h is stirred to react, EDTAP dipotassium ethylene diamine tetraacetate 1.6g is added, 70 DEG C are stirred to react 2h, obtain modified hypophosphorous acid
Manganese；
(2), with blender, condenser pipe, thermometer 500ml there-necked flasks in be added；Tetramethyl ammonium chloride 0.74g,
Polytetrahydrofuran ether glycol 70g and hexamethylene diisocyanate 30g, reacts 4h at 80 DEG C, obtains base polyurethane prepolymer for use as A,
The molecular weight of the polytetrahydrofuran ether glycol is 1000；
(3), trimethyl silanol 3.5g and methyl ethyl ketone 16.8g is added into performed polymer A, reacts 3.5h under the conditions of 75 DEG C,
Modification manganese hypophosphite 7.2g, 4- Carboxybenzeneboronic acid 3.6g and nitrilotriacetic acid 2.8g prepared by step (1), reaction temperature 85 is added
DEG C, reaction time 1h, addition triethylamine 14.5g progress neutralization reaction 60min, addition 4,8- dihydroxy quinoline -2- formic acid 2.8g,
Water 110g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
Example three
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
8.2g, boric acid 26.4g, diethanol amine 22.6g, hexamethylolmelamine 13g and benzilic acid 2.8g and water 55g,
PH to 4 is adjusted, 80 DEG C is heated to, is stirred to react 1h, EDTAP dipotassium ethylene diamine tetraacetate 0.9g, 60 DEG C are stirred to react 2h, are modified
Manganese hypophosphite；
(2), with blender, condenser pipe, thermometer 500ml there-necked flasks in, be added stearyl trimethyl ammonium chloride
0.52g, polytetrahydrofuran ether glycol 80g and hexamethylene diisocyanate 36g, react 2h at 70 DEG C, it is pre- to obtain polyurethane
The molecular weight of aggressiveness A, the polytetrahydrofuran ether glycol are 1000；
(3), nitrilotriacetic acid 2.6g and methyl ethyl ketone 21.4g is added into performed polymer A, reacts 2.5h under the conditions of 80 DEG C, adds
Enter modification manganese hypophosphite 7.9g, 4- Carboxybenzeneboronic acid 4.8g and diphenyl methane dimaleimide 3.6g of step (1) preparation, instead
85 DEG C, reaction time 3.5h of temperature is answered, triethylamine 16.2g is added and carries out neutralization reaction 40min, sodium salicylate 3.2g, water is added
160g stirrings carry out emulsification 1h, obtain the polyurethane coating of fire-retardant, waterproof and low VOC.
Example four
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
6.4g, boric acid 14g, diethanol amine 23.2g, hexaphenoxycyclotriphosphazene 9.5g and phloridzin 5.5g and water 80g adjust pH and arrive
4,80 DEG C are heated to, 2h is stirred to react, EDTAP dipotassium ethylene diamine tetraacetate 1.5g is added, 50 DEG C are stirred to react 3h, obtain modified phosphorus
Sour manganese；
(2), with blender, condenser pipe, thermometer 250ml there-necked flasks in triethyl aluminum 0.35g, poly- tetrahydrochysene is added
Furans ether glycol 60g and hexamethylene diisocyanate 20g, react 2h at 80 DEG C, obtain base polyurethane prepolymer for use as A, described poly-
The molecular weight of tetrahydrofuran ether glycol is 1000；
(3), nitrilotriacetic acid 0.52g and methyl ethyl ketone 9.2g is added into performed polymer A, reacts 3.5h under the conditions of 70 DEG C, adds
Enter modification manganese hypophosphite, 3.6g4- Carboxybenzeneboronic acids and the semicarbazides 2.6g of 4g steps (1) preparation, 80 DEG C of reaction temperature, reaction
Time 1h is added 7.5g triethylamines and carries out neutralization reaction 30min, and water 70g is added and is stirred emulsification 1h, obtains fire-retardant, waterproof
With the polyurethane coating of low VOC.
Example five
(1), the preparation of modified manganese hypophosphite：Manganese hypophosphite is added in the 250ml there-necked flasks with blender, thermometer
3.2g, boric acid 9g, diethanol amine 36g, melamine cyanurate 15g and benzilic acid 3.2g and water 80g adjust pH
To 4,70 DEG C are heated to, is stirred to react 2h, EDTAP dipotassium ethylene diamine tetraacetate 1.8g is added, 70 DEG C are stirred to react 2h, obtain modified time
Manganese phosphate；
(2), with blender, condenser pipe, thermometer 500ml there-necked flasks in isopropylmagnesium chloride 0.94g, poly- is added
Tetrahydrofuran ether glycol 100g and hexamethylene diisocyanate 50g, react 1h at 90 DEG C, obtain base polyurethane prepolymer for use as A, institute
The molecular weight for stating polytetrahydrofuran ether glycol is 2000；
(3), trimethyl silanol 4.2g and methyl ethyl ketone 25.5g is added into performed polymer A, reacts 3.5h under the conditions of 75 DEG C,
Modification manganese hypophosphite 9.9g, 4- Carboxybenzeneboronic acid 7.4g and tetraethylenepentamine 2.8g prepared by step (1), reaction temperature 95 is added
DEG C, reaction time 1h, addition triethylamine 15.5g progress neutralization reaction 60min, addition 4,8- dihydroxy quinoline -2- formic acid 3.7g,
Water 75g is stirred emulsification 1h, obtains the polyurethane coating of fire-retardant, waterproof and low VOC.
The advantageous effect further illustrated the present invention 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, waterproof 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/grade | 3 | 3 | 2 | 2 | 2 | 2 |
| Flexibility/mm | 2 | 3 | 3 | 3 | 3 | 2 |
From table two it can be found that from film outward appearance, hardness, adhesive force, flexibility better performances.
The mechanical property of film obtained by the polyurethane coating that table two is fire-retardant, water proofing property is with low VOC
The reference of two middle finger object detection method of table (Jiang Wei auspicious leather finish physical and chemical inspection [M] China Light Industry Press,
1999), film elongation at break, tensile strength obtained by coating of the present invention, wear-resistant performance are preferable.
Anti-flammability is referred to by smoke density method (maximum smoke density reaches the maximum smoke density time), oxygen index (OI), vertical combustion
(flaming combustion time, glowing time) is marked to weigh, elongation at break characterizes its mechanical property.
The anti-flammability of film obtained by the polyurethane coating that table three is fire-retardant, light resistance is with low VOC
The detection of three indices of table is respectively according to following standard：Smoke density is measured according to GB8323-2008, oxygen index (OI)
Using GB/T5454-1997《Textile combustion performance test-oxygen index method》It measures；Flaming combustion time and glowing time
It is by GB/T 5455-1997《Textile combustion can test-normal beam technique》To measure.
As shown in Table 3, when the present invention is burnt with sunproof polyurethane coating with film obtained by adhesive, maximum smoke density is aobvious
Writing reduces, and reaches the maximum smoke density time and significantly extends, oxygen index (OI) significantly improves, and burning time is obviously shortened.
It is tested according to limits of harmful substances standard in GB24408-2009 exterior coatings:
Table four is fire-retardant, waterproof and low VOC polyurethane coating VOC
Table five is fire-retardant, the wherein important performance of waterproof and the polyurethane coating of low VOC
Claims (10)
1. a kind of polyurethane coating, which is characterized in that the polyurethane coating prepare raw material and component includes：Azoformic acid
The equal three nitrogen borine 0.68g of dibenzyl ester 0.25g, polytetrahydrofuran ether glycol 72g, hexamethylene diisocyanate 18g, hexahydro, first
Ethyl ketone 8.8g, modified manganese hypophosphite 1g, 4- Carboxybenzeneboronic acid 3.2g, N- hydroxy thiosuccinimide 3.5g, triethylamine 7.8g
With water 70g.
2. polyurethane coating according to claim 1, which is characterized in that the modified manganese hypophosphite prepares raw material and group
Divide and includes：Manganese hypophosphite 11.2g, boric acid 25.6g, diethanol amine 28g, hexaphenoxycyclotriphosphazene 7.2g, phloridzin 2.8g, water
65g, EDTAP dipotassium ethylene diamine tetraacetate 1.6g.
3. polyurethane coating according to claim 1, which is characterized in that the modified manganese hypophosphite is made by the following method
It is standby：Be added in the 250ml there-necked flasks with blender, thermometer manganese hypophosphite 11.2g, boric acid 25.6g, diethanol amine 28g,
Hexaphenoxycyclotriphosphazene 7.2g and phloridzin 2.8g and water 65g adjusts pH to 4, is heated to 80 DEG C, is stirred to react 2h, add
Enter EDTAP dipotassium ethylene diamine tetraacetate 1.6g, 70 DEG C are stirred to react 1h, obtain modified manganese hypophosphite.
4. a kind of polyurethane coating, which is characterized in that the polyurethane coating prepare raw material and component includes：Tetramethyl chlorination
Ammonium 0.74g, polytetrahydrofuran ether glycol 70g, hexamethylene diisocyanate 30g, trimethyl silanol 3.5g, methyl ethyl ketone 16.8g,
Modified manganese hypophosphite 7.2g, 4- Carboxybenzeneboronic acid 3.6g, nitrilotriacetic acid 2.8g, triethylamine 14.5g, 4,8- dihydroxy quinoline -2-
Formic acid 2.8g and water 110g.
5. polyurethane coating according to claim 4, which is characterized in that the modified manganese hypophosphite prepares raw material and group
Divide and includes：Manganese hypophosphite 5.2g, boric acid 8g, diethanol amine 18g, benzilic acid 14g, 4- hydroxyphenethylamine 2.9g, water
70g, EDTAP dipotassium ethylene diamine tetraacetate 1.6g.
6. polyurethane coating according to claim 4, which is characterized in that the modified manganese hypophosphite is made by the following method
It is standby：Manganese hypophosphite 5.2g, boric acid 8g, diethanol amine 18g, hexichol are added in the 250ml there-necked flasks with blender, thermometer
Base glycolic 14g and 4- hydroxyphenethylamine 2.9g and water 70g adjust pH to 4, are heated to 60 DEG C, are stirred to react 2h, and second is added
Ethylenediamine tetraacetic acid (EDTA) dipotassium 1.6g, 70 DEG C are stirred to react 2h, obtain modified manganese hypophosphite.
7. a kind of polyurethane coating, which is characterized in that the polyurethane coating prepare raw material and component includes：Stearyl front three
Ammonium chloride 0.52g, polytetrahydrofuran ether glycol 80g, hexamethylene diisocyanate 36g, nitrilotriacetic acid 2.6g, methyl ethyl ketone
21.4g, modified manganese hypophosphite 7.9g, 4- Carboxybenzeneboronic acid 4.8g, diphenyl methane dimaleimide 3.6g, triethylamine 16.2g,
Sodium salicylate 3.2g and water 160g.
8. polyurethane coating according to claim 7, which is characterized in that the modified manganese hypophosphite prepares raw material and group
Divide and includes：Manganese hypophosphite 8.2g, boric acid 26.4g, diethanol amine 22.6g, hexamethylolmelamine 13g and benzilic acid
2.8g, water 55g, EDTAP dipotassium ethylene diamine tetraacetate 0.9g.
9. a kind of polyurethane coating, which is characterized in that the polyurethane coating prepare raw material and component includes：Triethyl aluminum
0.35g, polytetrahydrofuran ether glycol 60g and hexamethylene diisocyanate 20g, nitrilotriacetic acid 0.52g, methyl ethyl ketone 9.2g, change
Property manganese hypophosphite 4g, 4- Carboxybenzeneboronic acid 3.6g, semicarbazides 2.6g, triethylamine 7.5g and water 70g.
10. a kind of polyurethane coating, which is characterized in that the polyurethane coating prepare raw material and component includes：Isopropyl chloride
Change magnesium 0.94g, polytetrahydrofuran ether glycol 100g, hexamethylene diisocyanate 50g, trimethyl silanol 4.2g, methyl ethyl ketone
25.5g, modified manganese hypophosphite 9.9g, 4- Carboxybenzeneboronic acid 7.4g, tetraethylenepentamine 2.8g, triethylamine 15.5g, 4,8- dihydroxy
Quinoline -2- formic acid 3.7g and water 75g.
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| CN104109457A (en) * | 2014-08-12 | 2014-10-22 | 段小宁 | Preparation method of flame-retardant and waterproof aqueous polyurethane coating and adhesive |
| CN104356915A (en) * | 2014-11-29 | 2015-02-18 | 朱蕾 | Method for preparing flame-retardancy and waterproof aqueous polyurethane coating and adhesive |
| CN104861851A (en) * | 2015-05-05 | 2015-08-26 | 段宝荣 | Method for preparing flame retardant aqueous polyurethane coating and adhesive |
| CN105176368A (en) * | 2015-10-26 | 2015-12-23 | 烟台大学 | Preparation method of polyurethane coating and adhesive with flame retardance and light resistance |
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| CN103073696B (en) * | 2013-01-30 | 2014-08-13 | 段宝荣 | Preparation method of light-resistant waterborne polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104109457A (en) * | 2014-08-12 | 2014-10-22 | 段小宁 | Preparation method of flame-retardant and waterproof aqueous polyurethane coating and adhesive |
| CN104356915A (en) * | 2014-11-29 | 2015-02-18 | 朱蕾 | Method for preparing flame-retardancy and waterproof aqueous polyurethane coating and adhesive |
| CN104861851A (en) * | 2015-05-05 | 2015-08-26 | 段宝荣 | Method for preparing flame retardant aqueous polyurethane coating and adhesive |
| CN105176368A (en) * | 2015-10-26 | 2015-12-23 | 烟台大学 | Preparation method of polyurethane coating and adhesive with flame retardance and light resistance |
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