CN107151522A - Graphene is modified APP/PERM/EL aqueous polyurethanes anti-flaming dope and preparation method - Google Patents

Graphene is modified APP/PERM/EL aqueous polyurethanes anti-flaming dope and preparation method Download PDF

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CN107151522A
CN107151522A CN201710312458.4A CN201710312458A CN107151522A CN 107151522 A CN107151522 A CN 107151522A CN 201710312458 A CN201710312458 A CN 201710312458A CN 107151522 A CN107151522 A CN 107151522A
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graphene
parts
perm
molecular weight
app
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CN107151522B (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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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    • 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
    • C08G18/40—High-molecular-weight compounds
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08G18/6633—Compounds of group C08G18/42
    • 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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    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—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
    • 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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    • C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract

APP/PERM/EL aqueous polyurethanes anti-flaming dope and preparation method, method are modified the invention discloses graphene：(1) dry feedstock；(2) dry polycarbonate glycol, PTMG, PTMEG are mixed with isoflurane chalcone diisocyanate, reaction, plus dihydromethyl propionic acid, 1,6 hexylene glycols, trimethylolpropane, dibutyl tin dilaurate, the pyrrolidones of N methyl 2 and acetone, triethylamine is added, disperses, obtains aqueous polyurethane emulsion；(3) polyphosphoric acid amine, pentaerythrite and melamine are mixed, are added in graphene aqueous dispersions, centrifuged, obtain modified Intumescent Retardant System；(4) in hydrotropism's polyaminoester emulsion, plus modified Intumescent Retardant System, deionized water and absolute ethyl alcohol, centrifugation, solvent is removed, is produced.Paint coatings heat endurance of the present invention is good, good flame resistance, >=90% mass and original shape can be kept in 700 DEG C of air.From automatic distinguishing in burning things which may cause a fire disaster 5s.

Description

Graphene is modified APP/PERM/EL aqueous polyurethanes anti-flaming dope and preparation method
Technical field
APP/PERM/EL aqueous polyurethanes anti-flaming dope and preparation method are modified the present invention relates to a kind of graphene, is belonged to New function Material Field.
Background technology
Nowadays, aqueous polyurethane (WPU) as a kind of covering with paint high polymer material with premium properties woodenware, The field extensive use such as leather, fiber, textile, plastic products.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 is belonged to as the aqueous polyurethane of coating finishing agent Combustible material, tends to burning in use and the security of the lives and property to people causes heavy losses.Improve weaving The surcharge of product and become particularly important the need for meeting in terms of fabrics flame resistance.
Fireproof coating is also referred to as anti-flaming dope, and expanding fire-proof paint is a kind of main Types in such coating, at present Applied with APP (APP)/pentaerythrite (PERM)/melamine (EL) for the expansion fire-proof of Intumescent Retardant System (IFR) Material has been widely used in the fire prevention processing of steel construction and timber structure, and the system is mainly to be passed through by IFR thermal decomposition and IFR Esterification and dehydration carbonization reaction generate foamed char and reach fire-retardant and heat-insulated purpose.But because the flame-retardant system have it is residual The shortcomings of charcoal rate is low, high-temperature oxidation is poor, have impact on APP/PERM/EL coating fire protecting performances.
In recent years since, the research about graphene has obtained extensive concern.Graphene be one kind by carbon atom with hydridization Track composition hexangle type is in the planar structure of honeycomb lattice, the two-dimensional material of only one of which carbon atom thickness.Because it has height Electric conductivity, high-specific surface area, high-termal conductivity and excellent mechanical performance so that graphene be widely used in ultracapacitor, The fields such as clang ion battery, electronic component, memory device, erosion shield, absorbing material.
But not yet there is graphene to be modified the report of APP/PERM/EL aqueous polyurethane anti-flaming dopes at present.
The content of the invention
The purpose of the present invention is that the expandable flame retardant for overcoming prior art to exist has carbon yield is low, high-temperature oxidation is poor etc. Shortcoming there is provided a kind of heat endurance is good, fire resistance is good, carbon yield is low, deformation is small and residual quantity in 700 DEG C of air big, The graphene of 5s interior energy automatic distinguishings is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes.
Second object of the present invention is to provide a kind of graphene and is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes Preparation method.
Technical scheme is summarized as follows：
A kind of graphene is modified the preparation method of APP/PERM/EL aqueous polyurethane anti-flaming dopes, comprises the following steps：
(1) the poly- tetrahydrochysene furan that the PCDL for being respectively 1000-2000 by molecular weight, molecular weight are 1000-2000 Mutter ether glycol, molecular weight be 1000-2000 PTMEG, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6- oneself two Alcohol, trimethylolpropane and dibutyl tin dilaurate vacuum dehydration；METHYLPYRROLIDONE, acetone and triethylamine It is separately dried；
(2) mass fraction is pressed, the PCDL for being 1000-2000 by 3-4 parts molecular weight after step (1) processing, The polyethers two that PTMG that 0.8-1.2 parts of molecular weight are 1000-2000,1-1.5 parts of molecular weight are 1000-2000 Alcohol is well mixed with 9-10 parts of isoflurane chalcone diisocyanates, and stirring reaction 1.5-3h, is cooled to 40-50 at 80-100 DEG C DEG C, sequentially add 0.8-1 parts of dihydromethyl propionic acids, 2-2.5 parts 1,6- hexylene glycols, 0.5-0.6 part trimethylolpropane, 0.03- 0.04 part of dibutyl tin dilaurate, 100-200 parts of METHYLPYRROLIDONEs 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, adds 0.6-1 parts of triethylamines, dispersed with stirring 1-1.5h is prepared aqueous Polyaminoester emulsion；
(3) it is 1-3 in mass ratio by polyphosphoric acid amine, pentaerythrite and melamine：1-3：1-2 ratio mixing, obtains mixed Liquid is closed, is added in ultrasonic disperse 5-7h graphene aqueous dispersions, 8-12min is centrifuged under 7000-8000r/min, is made Modified Intumescent Retardant System, the mass ratio of the mixed liquor and graphene is 95-99：1-5；
(4) in mass ratio it is 28-30：10-12：29-31：In 29-31 ratio, hydrotropism's polyaminoester emulsion, addition changes Property Intumescent Retardant System, deionized water and absolute ethyl alcohol, at room temperature, 5000-6000r/min centrifuge 1-2min, decompression steam Solvent is removed in distillation, that is, is obtained graphene and be modified APP/PERM/EL aqueous polyurethane anti-flaming dopes, the APP is APP Abbreviation；PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine.
Polyphosphoric acid amine molecular weight is 1000-2000, phosphorus content 31%-32%.
A kind of graphene prepared by the above method is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes.
Advantages of the present invention：
The coating heat endurance that the graphene of the present invention is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes is good, fire-retardant Performance is good, carbon yield is low, deformation is small and the residual quantity in 700 DEG C of air big, be able to can be kept in 700 DEG C of air >= 90% mass simultaneously maintains original shape.Leave automatic distinguishing in burning things which may cause a fire disaster 5s.
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
Graphene is selected from Ningbo Mo Xi Science and Technology Ltd.s reinforced graphite alkene SE1430, other enterprise's lifes in each embodiment The property of the production graphene similar to 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 graphene is modified the preparation method of APP/PERM/EL aqueous polyurethane anti-flaming dopes, comprises the following steps：
(1) PTMG that the PCDL for being respectively 1000 by molecular weight, molecular weight are 1000, point Son amount is 1000 PTMEG, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6-HD, trimethylolpropane With dibutyl tin dilaurate vacuum dehydration；METHYLPYRROLIDONE, acetone and triethylamine are separately dried；
(2) press mass fraction, by step (1) processing after 3 parts of molecular weight for 1000 PCDL, 0.8 part point Son amount be 1000 PTMG, 1 part of molecular weight be 1000 PTMEG and 9 parts of isoflurane chalcone diisocyanates Well mixed, the stirring reaction 3h at 80 DEG C is 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 METHYLPYRROLIDONEs (acetone is zero), Reaction temperature is risen into 75 DEG C of reaction 3.5h, 20 DEG C is cooled to, adds 0.6 part of triethylamine, dispersed with stirring 1h is prepared aqueous Polyaminoester emulsion；
(3) it is 1 in mass ratio by polyphosphoric acid amine, pentaerythrite and melamine：1：1 ratio mixing, obtains mixed liquor, plus Enter into ultrasonic disperse 5h graphene aqueous dispersions, 12min is centrifuged under 7000r/min, modified expandable flame retardant body is made System, the mass ratio of the mixed liquor and graphene is 99：1；
(4) it is 28 in mass ratio:10:31:In 31 ratio, hydrotropism's polyaminoester emulsion, modified expandable flame retardant is added System, deionized water and absolute ethyl alcohol, at room temperature, 2min are centrifuged in 5000r/min, vacuum distillation removes solvent, that is, obtains stone Black alkene is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes.
The APP is the abbreviation of APP；PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine.
Polyphosphoric acid amine molecular weight is 1000, phosphorus content 31%.
Embodiment 2
A kind of graphene is modified the preparation method of APP/PERM/EL aqueous polyurethane anti-flaming dopes, comprises the following steps：
(1) PTMG that the PCDL for being respectively 2000 by molecular weight, molecular weight are 2000, point Son amount is 2000 PTMEG, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6-HD, trimethylolpropane With dibutyl tin dilaurate vacuum dehydration；METHYLPYRROLIDONE, acetone and triethylamine are separately dried；
(2) press mass fraction, by step (1) processing after 4 parts of molecular weight for 2000 PCDL, 1.2 parts points Son amount be 2000 PTMG, 1.5 parts of molecular weight be 2000 PTMEG and 10 parts of isocyanides of isophorone two Acid esters be well mixed, the stirring reaction 1.5h at 100 DEG C is cooled to 50 DEG C, sequentially add 1 part of dihydromethyl propionic acid, 2.5 part 1, 6- hexylene glycols, 0.6 part of trimethylolpropane, 0.04 part of dibutyl tin dilaurate, 200 parts of METHYLPYRROLIDONEs and 40 Part acetone, rises to 90 DEG C of reaction 2h by reaction temperature, is cooled to 30 DEG C, adds 1 part of triethylamine, dispersed with stirring 1.5h is prepared into To aqueous polyurethane emulsion；
(3) it is 3 in mass ratio by polyphosphoric acid amine, pentaerythrite and melamine：3：2 ratio mixing, obtains mixed liquor, plus Enter into ultrasonic disperse 7h graphene aqueous dispersions, 8min is centrifuged under 8000r/min, modified expandable flame retardant body is made System, the mass ratio of the mixed liquor and graphene is 95：5；
(4) it is 30 in mass ratio:12:29:In 29 ratio, hydrotropism's polyaminoester emulsion, modified expandable flame retardant is added System, deionized water and absolute ethyl alcohol, at room temperature, 1min are centrifuged in 6000r/min, vacuum distillation removes solvent, that is, obtains stone Black alkene is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes.
The APP is the abbreviation of APP；PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine.
Polyphosphoric acid amine molecular weight is 2000, phosphorus content 32%.
Embodiment 3
A kind of graphene is modified the preparation method of APP/PERM/EL aqueous polyurethane anti-flaming dopes, comprises the following steps：
(1) PTMG that the PCDL for being respectively 1000 by molecular weight, molecular weight are 2000, point Son amount is 2000 PTMEG, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6-HD, trimethylolpropane With dibutyl tin dilaurate vacuum dehydration；METHYLPYRROLIDONE, acetone and triethylamine are separately dried；
(2) mass fraction is pressed, PCDL, 1 part of molecule by 3 parts of molecular weight after step (1) processing for 1000 PTMEG and 10 parts of isoflurane chalcone diisocyanates that PTMG that amount is 2000,1 part of molecular weight are 2000 Well mixed, the stirring reaction 2.5h at 90 DEG C is 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 METHYLPYRROLIDONEs and 25 part third Ketone, rises to 80 DEG C of reaction 3h by reaction temperature, is cooled to 25 DEG C, adds 0.8 part of triethylamine, dispersed with stirring 1h prepares water Property polyaminoester emulsion；
(3) it is 2 in mass ratio by polyphosphoric acid amine, pentaerythrite and melamine：2：1 ratio mixing, obtains mixed liquor, plus Enter into ultrasonic disperse 6h graphene aqueous dispersions, 10min is centrifuged under 8000r/min, modified expandable flame retardant body is made System, the mass ratio of the mixed liquor and graphene is 97：3；
(4) it is 29 in mass ratio:11:30:In 30 ratio, hydrotropism's polyaminoester emulsion, modified expandable flame retardant is added System, deionized water and absolute ethyl alcohol, at room temperature, 2min are centrifuged in 5000r/min, vacuum distillation removes solvent, that is, obtains stone Black alkene is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes.
The APP is the abbreviation of APP；PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine.
Polyphosphoric acid amine 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:HRR peak value, unit W/g；THR:Total heat release, unit kj/g.
Graphene is given in table 2 and is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes quality damage in degradation process Lose 5% (T5%), 50% (T50%) and the biggest quality loss when temperature (Tmax)
Data are understood in analytical table 1, and graphene of the invention is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes and played Good fire retardation, heat endurance is good, fire resistance is good, carbon yield is low, and operating efficiency simple and easy to apply is high, technology effect Fruit is prominent, is had broad application prospects and practical value in terms of the fire safety of textile is improved.
Graphene obtained by 2 pairs of table is modified APP/PERM/EL aqueous polyurethanes anti-flaming dope and carries out thermogravimetric analysis, can be with >=90% mass can be kept in 700 DEG C of air and maintain original shape by finding out the coating of the present invention.
Above-described embodiment is only used for explaining the present invention, rather than limits the scope of the invention.In the spirit of the present 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. a kind of graphene is modified the preparation method of APP/PERM/EL aqueous polyurethane anti-flaming dopes, it is characterized in that including as follows Step：
(1) PTMG that the PCDL for being respectively 1000-2000 by molecular weight, molecular weight are 1000-2000 Glycol, molecular weight are 1000-2000 PTMEG, isoflurane chalcone diisocyanate, dihydromethyl propionic acid, 1,6-HD, Trimethylolpropane and dibutyl tin dilaurate vacuum dehydration；METHYLPYRROLIDONE, acetone and triethylamine difference Dry；
(2) mass fraction is pressed, PCDL, the 0.8- for being 1000-2000 by 3-4 parts molecular weight after step (1) processing The PTMEG that PTMG 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 well mixed, and stirring reaction 1.5-3h, is cooled to 40-50 DEG C at 80-100 DEG C, according to Secondary 0.8-1 parts of dihydromethyl propionic acids of addition, 2-2.5 parts 1,6- hexylene glycols, 0.5-0.6 part trimethylolpropane, 0.03-0.04 parts Dibutyl tin dilaurate, 100-200 part METHYLPYRROLIDONE and 0-40 parts of acetone, 75-90 DEG C is risen to by reaction temperature 2-3.5h is reacted, 20-30 DEG C is cooled to, 0.6-1 parts of triethylamines are added, dispersed with stirring 1-1.5h prepares aqueous polyurethane Emulsion；
(3) it is 1-3 in mass ratio by polyphosphoric acid amine, pentaerythrite and melamine：1-3：1-2 ratio mixing, obtains mixed liquor, It is added in ultrasonic disperse 5-7h graphene aqueous dispersions, 8-12min is centrifuged under 7000-8000r/min, modification is made Intumescent Retardant System, the mass ratio of the mixed liquor and graphene is 95-99：1-5；
(4) in mass ratio it is 28-30：10-12：29-31：In 29-31 ratio, hydrotropism's polyaminoester emulsion, modification is added Intumescent Retardant System, deionized water and absolute ethyl alcohol, at room temperature, 1-2min are centrifuged in 5000-6000r/min, vacuum distillation is removed Solvent is removed, that is, obtains graphene and is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes, the APP is the abbreviation of APP； PERM is the abbreviation of pentaerythrite；EL is the abbreviation of melamine.
2. according to the method described in claim 1, it is characterized in that the polyphosphoric acid amine molecular weight is 1000-2000, phosphorus content 31%-32%.
3. a kind of graphene prepared by the method for claim 1 or 2 is modified APP/PERM/EL aqueous polyurethane anti-flaming dopes.
CN201710312458.4A 2017-05-05 2017-05-05 The modified APP/PERM/EL aqueous polyurethane anti-flaming dope of graphene and preparation method Expired - Fee Related CN107151522B (en)

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CN116004047A (en) * 2022-12-19 2023-04-25 浙江圆融科技有限公司 Intumescent fire-retardant coating and preparation method thereof

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CN110551413A (en) * 2018-05-31 2019-12-10 庄继昌 Water-based environment-friendly nontoxic waterproof and fireproof coating
CN109251655A (en) * 2018-09-05 2019-01-22 镇江朝阳机电科技有限公司 A kind of novel bus and manufacturing process
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CN113667091A (en) * 2021-08-20 2021-11-19 昆山华阳新材料股份有限公司 Graphene/waterborne polyurethane composite material and preparation method and application thereof
CN114836993A (en) * 2022-04-21 2022-08-02 陕西科技大学 Flame-retardant hydrophobic biomass-based waterborne polyurethane coating and preparation method thereof
CN114907757A (en) * 2022-05-10 2022-08-16 亚振家居股份有限公司 Waterborne polyurethane flame-retardant composite material and preparation process thereof
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