CN107151522B - The modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene and preparation method - Google Patents

The modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene and preparation method Download PDF

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CN107151522B
CN107151522B CN201710312458.4A CN201710312458A CN107151522B CN 107151522 B CN107151522 B CN 107151522B CN 201710312458 A CN201710312458 A CN 201710312458A CN 107151522 B CN107151522 B CN 107151522B
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graphene
perm
molecular weight
aqueous polyurethane
parts
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CN107151522A (en
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乔建军
赵兴旺
李韡
许然然
财音青格乐
赵秀丽
吴昊
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
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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
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
    • C09D5/185—Intumescent paints
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Abstract

The invention discloses the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene and preparation method, methods: (1) dry feedstock；(2) dry polycarbonate glycol, polytetrahydrofuran ether glycol, polyetherdiol are mixed with isoflurane chalcone diisocyanate, reaction, add dihydromethyl propionic acid, 1,6- hexylene glycol, trimethylolpropane, dibutyl tin dilaurate, n-methyl-2-pyrrolidone and acetone, triethylamine is added, dispersion obtains aqueous polyurethane emulsion；(3) ammonium polyphosphate, pentaerythrite and melamine are mixed, is added in graphene aqueous dispersions, be centrifuged, obtain modified Intumescent Retardant System；(4) in hydrotropism's polyaminoester emulsion, add modified Intumescent Retardant System, deionized water and dehydrated alcohol, be centrifuged, remove solvent to get.Paint coatings thermal stability of the present invention is good, good flame resistance, >=90% mass and original shape is able to maintain in 700 DEG C of air.From automatic distinguishing in fire source 5s.

Description

The modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene and preparation method
Technical field
The present invention relates to a kind of modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene and preparation methods, belong to New function Material Field.
Background technique
Nowadays, aqueous polyurethane (WPU) as a kind of covering with paint high molecular material with excellent performance woodenware, The fields such as leather, fiber, textile, plastic products are widely applied.Such as aqueous polyurethane coating is applied as a kind of novel environment friendly Material is widely used in the top finish of textile, but textile and the aqueous polyurethane as coating finishing agent belong to Combustible material tends to burn and cause heavy losses to the security of the lives and property of people in use.Improve weaving The surcharge of product and need to become particularly important in terms of meeting fabrics flame resistance.
Fireproof coating is also referred to as anti-flaming dope, and expanding fire-proof paint is one of such coating main Types, at present It is applied with the expansion fire-proof that ammonium polyphosphate (APP)/pentaerythrite (PERM)/melamine (EL) is Intumescent Retardant System (IFR) Material has been widely used in the fire prevention processing of steel construction and timber structure, which mainly relies on the thermal decomposition of IFR and IFR to pass through Esterification and dehydration carbonization reaction generate foamed char and achieve the purpose that fire-retardant and heat-insulated.But because the flame-retardant system is with residual The disadvantages of charcoal rate is low, high-temperature oxidation is poor affects APP/PERM/EL coating fire protecting performance.
In recent years since, the research in relation to graphene has obtained extensive concern.Graphene be one kind by carbon atom with hydridization Track forms the planar structure that hexangle type is in honeycomb lattice, the two-dimensional material of only one carbon atom thickness.Since it has height Electric conductivity, high-specific surface area, high-termal conductivity and excellent mechanical performance so that graphene be widely used in supercapacitor, The fields such as clang ion battery, electronic component, memory device, erosion shield, absorbing material.
But there has been no the reports of the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene at present.
Summary of the invention
The purpose of the present invention is overcome expandable flame retardant of the existing technology to have carbon yield is low, high-temperature oxidation is poor etc. Disadvantage, provides that a kind of thermal stability is good, flame retardant property is good, carbon yield is low, deformation is small and residual quantity in 700 DEG C of air is big, The modified APP/PERM/EL aqueous polyurethane anti-flaming dope of the graphene of energy automatic distinguishing in 5s.
A second object of the present invention is to provide a kind of modified APP/PERM/EL aqueous polyurethane anti-flaming dopes of graphene Preparation method.
Technical solution of the present invention is summarized as follows:
A kind of preparation method of the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene, includes the following steps:
(1) respectively by molecular weight be 1000-2000 polycarbonate glycol, molecular weight be 1000-2000 poly- tetrahydro furan Mutter ether glycol, molecular weight be the polyetherdiol of 1000-2000, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6- oneself two Alcohol, trimethylolpropane and dibutyl tin dilaurate vacuum dehydration；N-methyl-2-pyrrolidone, acetone and triethylamine It is separately dried；
(2) press mass fraction, by step (1) treated 3-4 part molecular weight for 1000-2000 polycarbonate glycol, The polyethers two that polytetrahydrofuran ether glycol that 0.8-1.2 parts of molecular weight are 1000-2000,1-1.5 parts of molecular weight are 1000-2000 Alcohol is uniformly mixed with 9-10 parts of isoflurane chalcone diisocyanates, is stirred to react 1.5-3h at 80-100 DEG C, is cooled to 40-50 DEG C, sequentially add 0.8-1 parts of dihydromethyl propionic acids, 2-2.5 part 1,6- hexylene glycol, 0.5-0.6 part trimethylolpropane, 0.03- 0.04 part of dibutyl tin dilaurate, 100-200 parts of n-methyl-2-pyrrolidone and 0-40 parts of acetone, reaction temperature is risen to 75-90 DEG C of reaction 2-3.5h is cooled to 20-30 DEG C, and 0.6-1 parts of triethylamines are added, is dispersed with stirring 1-1.5h, is prepared aqueous Polyaminoester emulsion；
(3) ratio that ammonium polyphosphate, pentaerythrite and melamine are 1-3:1-3:1-2 in mass ratio is mixed, is obtained mixed Liquid is closed, is added in the graphene aqueous dispersions of ultrasonic disperse 5-7h, is centrifuged 8-12min at 7000-8000r/min, is made The mass ratio of modified Intumescent Retardant System, the mixed liquor and graphene is 95-99:1-5；
It (4) is in mass ratio the ratio of 28-30:10-12:29-31:29-31, in hydrotropism's polyaminoester emulsion, addition changes Property Intumescent Retardant System, deionized water and dehydrated alcohol, at room temperature, 5000-6000r/min be centrifuged 1-2min, decompression steam Distillation goes solvent to get to the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene, and the APP is ammonium polyphosphate Abbreviation；PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine.
Ammonium polyphosphate molecular weight is 1000-2000, phosphorus content 31%-32%.
A kind of modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene of above method preparation.
Advantages of the present invention:
The coating thermal stability of the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene of the invention is good, fire-retardant Performance is good, carbon yield is low, deformation is small and residual quantity in 700 DEG C of air is big, can be able to maintain in 700 DEG C of air >= 90% mass simultaneously maintains original shape.Leave automatic distinguishing in fire source 5s.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
Graphene is selected from Ningbo Mo Xi Science and Technology Ltd. reinforced graphite alkene SE1430 in each embodiment, and other enterprises are raw The property of production graphene similar with above-mentioned graphene can be used for the present invention, i.e., the source of above-mentioned graphene is not to this hair It is bright to be defined.
Embodiment 1
A kind of preparation method of the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene, includes the following steps:
(1) respectively by molecular weight be 1000 polycarbonate glycol, molecular weight be 1000 polytetrahydrofuran ether glycol, point Son measures the polyetherdiol for 1000, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6-HD, trimethylolpropane With dibutyl tin dilaurate vacuum dehydration；N-methyl-2-pyrrolidone, acetone and triethylamine are separately dried；
(2) press mass fraction, by step (1) treated 3 parts of molecular weight be 1000 polycarbonate glycol, 0.8 part point Son measures the polytetrahydrofuran ether glycol for 1000, the polyetherdiol that 1 part of molecular weight is 1000 and 9 parts of isoflurane chalcone diisocyanates Be uniformly mixed, be stirred to react 3h at 80 DEG C, be cooled to 40 DEG C, sequentially add 0.8 part of dihydromethyl propionic acid, 2 parts of 1,6- oneself two Alcohol, 0.5 part of trimethylolpropane, 0.03 part of dibutyl tin dilaurate, 100 parts of n-methyl-2-pyrrolidone (acetone zero), Reaction temperature is risen into 75 DEG C of reaction 3.5h, 20 DEG C is cooled to, 0.6 part of triethylamine is added, is dispersed with stirring 1h, is prepared aqueous Polyaminoester emulsion；
(3) ratio that ammonium polyphosphate, pentaerythrite and melamine are 1:1:1 in mass ratio is mixed, obtains mixed liquor, It is added in the graphene aqueous dispersions of ultrasonic disperse 5h, is centrifuged 12min at 7000r/min, modified expandable flame retardant is made The mass ratio of system, the mixed liquor and graphene is 99:1；
(4) it is in mass ratio the ratio of 28:10:31:31, in hydrotropism's polyaminoester emulsion, modified expandable flame retardant is added System, deionized water and dehydrated alcohol are centrifuged 2min in 5000r/min, vacuum distillation removes solvent to get stone is arrived at room temperature The modified APP/PERM/EL aqueous polyurethane anti-flaming dope of black alkene.
The APP is the abbreviation of ammonium polyphosphate；PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine.
Ammonium polyphosphate molecular weight is 1000, phosphorus content 31%.
Embodiment 2
A kind of preparation method of the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene, includes the following steps:
(1) respectively by molecular weight be 2000 polycarbonate glycol, molecular weight be 2000 polytetrahydrofuran ether glycol, point Son measures the polyetherdiol for 2000, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6-HD, trimethylolpropane With dibutyl tin dilaurate vacuum dehydration；N-methyl-2-pyrrolidone, acetone and triethylamine are separately dried；
(2) press mass fraction, by step (1) treated 4 parts of molecular weight be 2000 polycarbonate glycol, 1.2 parts points Son measures the polytetrahydrofuran ether glycol for 2000, the polyetherdiol that 1.5 parts of molecular weight are 2000 and 10 parts of two isocyanides of isophorone Acid esters is uniformly mixed, and is stirred to react 1.5h at 100 DEG C, is cooled to 50 DEG C, sequentially adds 1 part of dihydromethyl propionic acid, 2.5 parts 1,6- hexylene glycol, 0.6 part of trimethylolpropane, 0.04 part of dibutyl tin dilaurate, 200 parts of n-methyl-2-pyrrolidone and Reaction temperature is risen to 90 DEG C of reaction 2h, is cooled to 30 DEG C, 1 part of triethylamine is added, is dispersed with stirring 1.5h by 40 parts of acetone, preparation Obtain aqueous polyurethane emulsion；
(3) ratio that ammonium polyphosphate, pentaerythrite and melamine are 3:3:2 in mass ratio is mixed, obtains mixed liquor, It is added in the graphene aqueous dispersions of ultrasonic disperse 7h, is centrifuged 8min at 8000r/min, modified expandable flame retardant body is made The mass ratio of system, the mixed liquor and graphene is 95:5；
(4) it is in mass ratio the ratio of 30:12:29:29, in hydrotropism's polyaminoester emulsion, modified expandable flame retardant is added System, deionized water and dehydrated alcohol are centrifuged 1min in 6000r/min, vacuum distillation removes solvent to get stone is arrived at room temperature The modified APP/PERM/EL aqueous polyurethane anti-flaming dope of black alkene.
The APP is the abbreviation of ammonium polyphosphate；PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine.
Ammonium polyphosphate molecular weight is 2000, phosphorus content 32%.
Embodiment 3
A kind of preparation method of the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene, includes the following steps:
(1) respectively by molecular weight be 1000 polycarbonate glycol, molecular weight be 2000 polytetrahydrofuran ether glycol, point Son measures the polyetherdiol for 2000, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6-HD, trimethylolpropane With dibutyl tin dilaurate vacuum dehydration；N-methyl-2-pyrrolidone, acetone and triethylamine are separately dried；
(2) press mass fraction, by step (1) treated 3 parts of molecular weight be 1000 polycarbonate glycol, 1 part of molecule Measure the polytetrahydrofuran ether glycol for 2000, the polyetherdiol that 1 part of molecular weight is 2000 and 10 parts of isoflurane chalcone diisocyanates Be uniformly mixed, be stirred to react 2.5h at 90 DEG C, be cooled to 45 DEG C, sequentially add 0.9 part of dihydromethyl propionic acid, 2 parts of 1,6- oneself Glycol, 0.5 part of trimethylolpropane, 0.03 part of dibutyl tin dilaurate, 170 parts of n-methyl-2-pyrrolidone and 25 part third Reaction temperature is risen to 80 DEG C of reaction 3h, is cooled to 25 DEG C, 0.8 part of triethylamine is added, is dispersed with stirring 1h, water is prepared by ketone Property polyaminoester emulsion；
(3) ratio that ammonium polyphosphate, pentaerythrite and melamine are 2:2:1 in mass ratio is mixed, obtains mixed liquor, It is added in the graphene aqueous dispersions of ultrasonic disperse 6h, is centrifuged 10min at 8000r/min, modified expandable flame retardant is made The mass ratio of system, the mixed liquor and graphene is 97:3；
(4) it is in mass ratio the ratio of 29:11:30:30, in hydrotropism's polyaminoester emulsion, modified expandable flame retardant is added System, deionized water and dehydrated alcohol are centrifuged 2min in 5000r/min, vacuum distillation removes solvent to get stone is arrived at room temperature The modified APP/PERM/EL aqueous polyurethane anti-flaming dope of black alkene.
The APP is the abbreviation of ammonium polyphosphate；PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine.
Ammonium polyphosphate molecular weight is 2000, phosphorus content 32%.
Table 1
Sample PHRR(W/g) THR(kj/g)
Blank sample 388 12.2
Embodiment 1 121 3.4
Embodiment 2 133 3.6
Embodiment 3 110 2.9
Table 2
Sample T5%(℃) T50%(℃) Tmax(℃)
Blank sample 455 567 589
Embodiment 1 685 742 759
Embodiment 2 675 732 739
Embodiment 3 689 745 762
In table 1: PHRR: heat release rate peak value, unit W/g；THR: total heat release, unit kj/g.
The modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene quality in degradation process is given in table 2 to damage Lose 5% (T5%), 50% (T50%) and the biggest quality lose when temperature (Tmax)
In analytical table 1 known to data, the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene of the invention is played Good fire retardation, thermal stability is good, flame retardant property is good, carbon yield is low, and simple and easy operating efficiency is high, technology effect Fruit is prominent, has broad application prospects in terms of the fire safety for improving textile and practical value.
Table 2 carries out thermogravimetric analysis to the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of obtained graphene, can be with Find out that coating of the invention is able to maintain >=90% mass in 700 DEG C of air and maintains original shape.
Above-described embodiment is only used to explain the present invention, rather than limits the scope of the invention.In spirit of the invention Any equivalent change or modification made in essence and claims is all considered as within the scope of the present invention.

Claims (3)

1. the preparation method of the modified APP/PERM/EL aqueous polyurethane anti-flaming dope of a kind of graphene, it is characterized in that including as follows Step:
(1) respectively by molecular weight be 1000-2000 polycarbonate glycol, molecular weight be 1000-2000 polytetrahydrofuran ether Glycol, molecular weight be the polyetherdiol of 1000-2000, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6-HD, Trimethylolpropane and dibutyl tin dilaurate vacuum dehydration；N-methyl-2-pyrrolidone, acetone and triethylamine difference It is dry；
(2) mass fraction is pressed, polycarbonate glycol, 0.8- by step (1) treated 3-4 part molecular weight for 1000-2000 The polyetherdiol that polytetrahydrofuran ether glycol that 1.2 parts of molecular weight are 1000-2000,1-1.5 parts of molecular weight are 1000-2000 with 9-10 parts of isoflurane chalcone diisocyanates are uniformly mixed, and are stirred to react 1.5-3h at 80-100 DEG C, are cooled to 40-50 DEG C, according to 0.8-1 parts of dihydromethyl propionic acids of secondary addition, 2-2.5 part 1,6- hexylene glycol, 0.5-0.6 part trimethylolpropane, 0.03-0.04 parts Dibutyl tin dilaurate, 100-200 part n-methyl-2-pyrrolidone and 0-40 parts of acetone, rise to 75-90 DEG C for reaction temperature 2-3.5h is reacted, is cooled to 20-30 DEG C, 0.6-1 parts of triethylamines are added, is dispersed with stirring 1-1.5h, aqueous polyurethane is prepared Lotion；
(3) ratio that ammonium polyphosphate, pentaerythrite and melamine are 1-3:1-3:1-2 in mass ratio is mixed, obtains mixed liquor, It is added in the graphene aqueous dispersions of ultrasonic disperse 5-7h, is centrifuged 8-12min at 7000-8000r/min, modification is made The mass ratio of Intumescent Retardant System, the mixed liquor and graphene is 95-99:1-5；
(4) in hydrotropism's polyaminoester emulsion, modified Intumescent Retardant System, deionized water and dehydrated alcohol is added, at room temperature, 5000-6000r/min is centrifuged 1-2min, and vacuum distillation removes solvent and is modified the aqueous poly- ammonia of APP/PERM/EL to get to graphene Ester anti-flaming dope, the APP are the abbreviation of ammonium polyphosphate；PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine, institute The mass ratio for stating aqueous polyurethane emulsion, the Intumescent Retardant System of modification, deionized water and dehydrated alcohol is 28-30:10-12: 29-31:29-31.
2. according to the method described in claim 1, it is characterized in that the ammonium polyphosphate molecular weight is 1000-2000, phosphorus content 31%-32%.
3. a kind of modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene prepared by the method for claims 1 or 2.
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