CN105238418A - Aqueous halogen-free fire retardant, and preparation method and application thereof - Google Patents

Aqueous halogen-free fire retardant, and preparation method and application thereof Download PDF

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Publication number
CN105238418A
CN105238418A CN201510591605.7A CN201510591605A CN105238418A CN 105238418 A CN105238418 A CN 105238418A CN 201510591605 A CN201510591605 A CN 201510591605A CN 105238418 A CN105238418 A CN 105238418A
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fire retardant
water
acid
halogen
free fire
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CN105238418B (en
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王玉忠
徐英俊
饶文辉
杨君驰
廖望
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Sichuan University
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Sichuan University
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Abstract

A disclosed aqueous halogen-free fire retardant has at least one of the structure general formulas shown in the specification. The fire retardant is prepared according to the following method: firstly adding A mol of an amino silane coupling agent into excess water at normal temperature, then dropwise adding B mol of a water solution or an ethanol and water solution of a phosphorus-containing organic acid or inorganic acid with stirring, continuing to stir for reaction for 2-12 h after dropwise adding is finished, and doing nothing or evaporating the solvent, so as to obtain the fire retardant, wherein 0<B<=3A. The invention also discloses application of the aqueous halogen-free fire retardant. The disclosed aqueous halogen-free fire retardant is good in stability at normal temperature, long in storage period and high in fire-retardation efficiency, and releases less toxic smoke amount during combustion. The preparation technology is simple, easy to control, and free of organic solvents. No toxic substances are discharged during preparation and usage, preparation and application are green and free of pollution, and industrialization is facilitated. Also, the fire retardant is good in compatibility with various materials, is colorless or light-colored and transparent, and is not high in usage amount and relatively wide in application scope.

Description

Water-based halogen-free fire retardant and its preparation method and application
Technical field
The invention belongs to aqueous fire retardant and Synthesis and applications technical field thereof, be specifically related to a kind of water-based halogen-free fire retardant and its preparation method and application.
Background technology
Macromolecular material electrical insulating property is good, the good machine-shaping simultaneously of chemical stability is convenient, is thus widely used.But its inflammableness but limits its application in more areas, as electron device, the fire-retardant ornament etc. protecting clothes and particular place.The use of fire retardant often effectively can promote the flame retardant properties of all kinds of macromolecular material, widens its range of application.
When fire occurs, Halogen fire retardant material often produces a large amount of smog and poisonous corrosive hydrogen halides gas in fire-retardant process, causes secondary to endanger.European Union has promulgated RoHs instruction in succession namely about limiting in electronic electric equipment and prohibitting the use the instruction of some poisonous and harmful substances and element and WEEE instruction namely about the electric waste of control, realizes the instruction of recycling and the utilization of other forms.The national standard of the China also multiple material of construction of declaration and product burns performance rate, this standard and above-mentioned European Union new standard have common feature, in evaluating material flame retardant properties, namely emphasize that heat release puts speed, fire spread speed, the corrodibility of giving birth to cigarette and products of combustion and toxicity etc.On this type of new standard of reply, traditional halogenated flame retardant seems helpless, uses the halogen-free flame retardants of efficient, low cigarette, nontoxic or low toxicity will become the inexorable trend of following fire retardant material development.Particularly, because of objectionable impurities lower in preparation and use procedure release, water-based halogen-free fire retardant has become the focus in the study hotspot of this area.
CN201510159130 reports a kind of water expansion wood fire retardant and preparation method thereof, and this fire retardant is by the water-soluble terpolymers of one and melamino-formaldehyde performed polymer is composite forms.Wherein terpolymers is by carbon source, source of the gas, and acid source copolymerization forms, and melamino-formaldehyde performed polymer is synthesized by trimeric cyanamide and formaldehyde.In combustion, water-soluble terpolymers can be catalyzed into carbon to this fire retardant, and expansion molding, block inflammable gas and heat.Melamino-formaldehyde performed polymer can in wood surface generation polycondensation in steeping process, by this water expansion wood fire retardant " lock " of being impregnated in timber wherein, has both prevented it anti-white, and can supplement certain carbon source again.Though it is high that this fire retardant has pH, good water solubility, sample load factor is high, the features such as flame retardant effect is excellent, but need now with the current, can not preserve for a long time, and in preparation and use procedure, all can there is the problem of Form aldehyde release, its application prospect is very limited.
CN201310154731 discloses a kind of linear preparation method of water-based Synthesis, Characterization of Polyphosphazenes fire retardant and the application in co-mix-modified flame-retardant adhesive film thereof; its concrete preparation method is: first get hexachlorocyclotriphosphazene under vacuum 220-260 DEG C of polymerization within 4-8 hour, prepare linear polydichlorophosphazenes; be dissolved in again in tetrahydrofuran (THF) from multiple different sodium alkoxide; under nitrogen protection, to purify to obtain after reacting 5-12 hour at 30-60 DEG C product.This linear water-based Synthesis, Characterization of Polyphosphazenes fire retardant is not halogen-containing and not containing formaldehyde, ignition-proof element the content of nitrogen and phosphorous is high, the efficient and low toxicity of flame retardant effect, flame retardant resistance viscose film can be prepared with viscose glue blending, the features such as the viscose film after process has good flame resistance, is not fuming, and durability of fire-retardant energy is excellent.But this fire retardant preparation method is comparatively complicated, the required condition of preparation is comparatively harsh, being difficult to realize extension and producing, and preparation process needs to use a large amount of organic solvent, and cost is high and not environmentally.
Summary of the invention
The object of the invention is for the some shortcomings existing for prior art, first a kind of new water-based halogen-free fire retardant is provided.
Secondary objective of the present invention is to provide the preparation method of above-mentioned water-based halogen-free fire retardant.
Another object of the present invention is to provide the application of above-mentioned water-based halogen-free fire retardant.
Water-based halogen-free fire retardant provided by the invention is a kind of polysiloxane ammonium salt of phosphoric acid, is specially at least one in following general structure:
R in formula is CH 3, OCH 3, OC 2h 5or OH, x and y be more than or equal to 0 but be asynchronously 0 integer, m and n is 0,1 or 2, can identical also can not be identical, 0 < a≤(m+1) x+ (n+1) y.
The method of the above-mentioned water-based halogen-free fire retardant of preparation provided by the invention, the method is at normal temperatures, first Amol amino silicane coupling agent is added in excessive water, then the phosphorous water of acid of Bmol or the solution of second alcohol and water is dripped while stirring, dripping off rear continuation stirring reaction obtains colourless to flaxen transparent liquid after 2-12 hour, or steaming obtains colourless to yellow transparent solid or thick liquid after desolventizing again, wherein 0 < B≤3A, namely in the added water of phosphorous acid or the solution of second alcohol and water, the molar weight of phosphoric acid can not exceed the primary amine of amino silicane coupling agent and the molar weight of secondary amine.
In above method, the ratio of A and B is preferably A:B=1-2:1.
In above method, amino silicane coupling agent used is γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, γ-(quadrol base) propyl trimethoxy silicane, γ (-quadrol base) propyl-triethoxysilicane, γ-(quadrol base) hydroxypropyl methyl dimethoxysilane, γ (-quadrol base) hydroxypropyl methyl diethoxy silane, diethylenetriamine base propyl trimethoxy silicane, diethylenetriamine base propyl-triethoxysilicane, at least one in γ-(diethylenetriamine base) hydroxypropyl methyl dimethoxysilane and γ-(diethylenetriamine base) hydroxypropyl methyl diethoxy silane.
The phosphorous acid used of above method is at least one in Hypophosporous Acid, 50, phenyl phosphinic acid, diphenyl phosphonic acid, 10-hydroxyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-OH), phosphorous acid, phenyl-phosphonic acid and 2-carboxyethyl phenyl Hypophosporous Acid, 50 (CEPPA) and phosphoric acid.
The application of water-based halogen-free fire retardant provided by the invention is the application in flame retarded polymeric material, especially carrys out the macromolecule matrix materials such as resistance combustion polyurethane foam, use for synthetic leather polyurethane slurry, epoxy resin, polyolefin wood plastic compound and polyvinyl alcohol as flame-retardant additive.
The application of water-based halogen-free fire retardant provided by the invention is the application in flame-retardant textile, timber or paper, specifically the fire-retardant treatment liquid of wherein gained is used for the matrixes such as flame-retardant textile, timber and paper.
Compared with prior art, tool has the following advantages in the present invention:
1, because water-based halogen-free fire retardant provided by the invention is obtained by aminosilane and phosphorous organic or inorganic acid direct reaction, wherein do not add other component, even if when it is silicon sol solution in addition, also can stablize at normal temperatures and keep clear to store more than 6 months, thus not only have good can be depot, can produce in a large number as a kind of product with shelf life, make it to apply widely, and also avoid the problem that prior art has Form aldehyde release in preparation and use procedure.
2, owing to containing the common ignition-proof element of phosphorus, nitrogen and silicon three kinds in water-based halogen-free fire retardant provided by the invention simultaneously, it can either promote that self and base material become charcoal rapidly on surface, enable the carbon-coating of the densification of formation intercept flame to continue to spread, also there is certain gas phase flame retardant effect simultaneously, in addition it is not containing other composition, as organic film-forming resin, thus it not only has good flame retardant effect, and poison gas burst size is less in combustion.
3, because water-based halogen-free fire retardant provided by the invention belongs to hybrid inorganic-organic materials, the continuous homogeneous phase in form, and colourless or light-coloured transparent, good with various types of materials consistency, often usage quantity is not high yet, thus can make its effectively promote Flame Retardancy can prerequisite under to its outward appearance and Effect on Mechanical Properties less, be conducive to expanding its range of application.
4, because preparation method provided by the invention is at normal temperatures, by amino silicane coupling agent and phosphorous acid with water or second alcohol and water for solvent Keep agitation a few hours or steam solvent again and carry out, the required mild condition of reaction, raw materials usedly be mostly industrial goods, in addition without the need to using a large amount of organic solvents, thus its preparation technology simple, ripe, be easy to control, energy consumption is low, environmental protection and with low cost, be beneficial to and realize industrialization.
5, because water-based halogen-free fire retardant provided by the invention is a kind of silicon sol solution, it had both had good flame retardant efficiency, it is again a kind of good filmogen, can when separately not adding organic film-forming resin, homogeneously can be coated on fabric face and form water white transparency or light yellow clear film, thus on the outward appearance of finish fabric and feel impact all less.
Accompanying drawing explanation
Fig. 1 is with D by gained film after the water-based halogen-free anti-flaming dope oven dry slaking prepared by the embodiment of the present invention 5 2o is nucleus magnetic hydrogen spectrum and the phosphorus spectrum of solvent gained.
Fig. 2 is the digital photograph before and after the water-based halogen-free fire retardant solvent evaporate to dryness prepared by the embodiment of the present invention 5, and this aqueous fire retardant is water white transparency homogeneous phase as seen.
Fig. 3 is the digital photograph of the fire retarding epoxide resin prepared by application examples 10 of the present invention, and it has the very high transparency as seen.
Fig. 4 is the scanning electron microscope (SEM) photograph (b) processing the flame-proof cotton fabric of gained in the scanning electron microscope (SEM) photograph (a) of untreated cotton fabric in comparative example 7 of the present invention and application examples 25.Can find that from figure anti-flaming dope is homogeneous phase continuous thin film shape material in the formation of cotton-textile fibres surface after fire retardant process, because it is thin and homogeneous, thus less on fabric feeling impact.
Embodiment
Embodiment given below is so that the invention will be further described.What be necessary to herein means out is that following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to scope.
What deserves to be explained is: 1) in following application examples, material number used is weight part; 2) fabric utilizing fire retardant to arrange, paper and timber, fire retardant charge capacity (gain in weight)=(quality after process-quality before treatment)/quality × 100% before treatment; 3) limiting oxygen index(LOI) of halogen-free anti-inflaming polyurethane foam, use for synthetic leather polyurethane slurry, epoxy resin, polyolefin wood moulding material, polyvinyl alcohol, fabric, paper and timber prepared of following application examples is with reference to GB/T2406.2-2009 standard testing; The vertical combustion grade of halogen-free flameproof flexible PU foam is with reference to (CalT.B.117A) standard testing of markon's welfare sub-technology bulletin 117A part, the vertical combustion grade of halogen-free flameproof paper is with reference to GB/T14656-93 standard testing, and remaining vertical combustion grade and horizontal firing grade are with reference to UL-94 standard testing.
Embodiment 1
At normal temperatures, first 0.5mol (89.7g) γ-aminopropyltrimethoxysilane is added in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.5mol (33.0g) Hypophosporous Acid, 50 is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 2 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 2
At normal temperatures, first 0.10mol (19.1g) γ-aminopropyltriethoxy diethoxy silane is added in 0.3L deionized water, then the 0.1L aqueous solution being dissolved with 0.05mol (7.1g) phenyl Hypophosporous Acid, 50 is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 4 hours, obtain water white sol solution, or again steam desolventize after colorless transparent viscous liquid.
Embodiment 3
At normal temperatures, first 0.3mol (57.8g) γ-aminopropyltrimethoxysilane is added in 0.2L deionized water, then the solution being dissolved with the 0.3L second alcohol and water of 0.3mol (69.6g) DOPO-OH is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 10 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 4
At normal temperatures, first 0.10mol (22.1g) γ-aminopropyl triethoxysilane is added in 0.1L deionized water, then the solution being dissolved with the 0.1L second alcohol and water of 0.05mol (11.6g) DOPO-OH is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 10 hours, obtain colourless sol solution, or again steam desolventize after water white solid.
Embodiment 5
At normal temperatures, first 0.8mol (177.1g) γ-aminopropyl triethoxysilane is added in 0.3L deionized water, then the 0.2L aqueous solution being dissolved with 0.8mol (65.6g) phosphorous acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 6
At normal temperatures, first by 1.0mol (222.3g) γ-(quadrol base) propyl trimethoxy silicane adds in 0.5L deionized water, then the solution being dissolved with the 0.2L second alcohol and water of 0.5mol (79.0g) phenyl-phosphonic acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 8 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 7
At normal temperatures, first by 0.4mol (88.9g) γ-(quadrol base) propyl trimethoxy silicane adds in 0.2L deionized water, then the aqueous solution being dissolved with the 0.1L of 0.2mol (13.2g) Hypophosporous Acid, 50 is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 10 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 8
At normal temperatures, first by 0.50mol (131.1g) γ-(quadrol base) propyl-triethoxysilicane adds in 0.3L deionized water, then the 0.1L aqueous solution being dissolved with 0.25mol (24.5g) phosphoric acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 8 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 9
At normal temperatures, first by 0.06mol (12.4g) γ-(quadrol base) hydroxypropyl methyl dimethoxysilane adds in the 0.1L aqueous solution, then the solution being dissolved with the 0.05L second alcohol and water of 0.02mol (4.4g) diphenyl phosphonic acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 12 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the viscous liquid of yellow transparent.
Embodiment 10
At normal temperatures, first by 0.3mol (69.7g) γ-(quadrol base) hydroxypropyl methyl diethoxy silane adds in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.3mol (19.8g) Hypophosporous Acid, 50 is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 4 hours, obtain water white sol solution, or steam again desolventize after the viscous liquid of yellow transparent.
Embodiment 11
At normal temperatures, first 0.1mol (26.5g) diethylenetriamine base propyl trimethoxy silicane is added in 0.1L deionized water, then drip while stirring and be dissolved with the 0.1L water of 0.1mol (23.2g) DOPO-OH and the solution of ethanol, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 12
At normal temperatures, first 0.4mol (106.2g) diethylenetriamine base propyl trimethoxy silicane is added in 0.4L deionized water solution, then drip while stirring and be dissolved with the 0.1L water of 0.2mol (43.6g) diphenyl phosphonic acid and the solution of ethanol, drip rear continuation at normal temperatures stirring reaction within 8 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 13
At normal temperatures, first 0.3mol (91.6g) diethylenetriamine base propyl-triethoxysilicane is added in 0.3L deionized water solution, then the 0.1L aqueous solution being dissolved with 0.1mol (21.4g) CEPPA is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain the sol solution of light yellow clear, or steam again desolventize after the solid of yellow transparent.
Embodiment 14
At normal temperatures, first by 0.2mol (49.9g) γ-(diethylenetriamine base) hydroxypropyl methyl dimethoxysilane adds in the 0.2L aqueous solution, then the 0.1L aqueous solution being dissolved with 0.1mol (15.8g) phenyl-phosphonic acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the thick solid of yellow transparent.
Embodiment 15
At normal temperatures, first by 0.1mol (27.5g) γ-(diethylenetriamine base) hydroxypropyl methyl diethoxy silane adds in the 0.1L aqueous solution, then the 0.1L aqueous solution being dissolved with 0.3mol (19.8g) Hypophosporous Acid, 50 is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 4 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 16
At normal temperatures, first 0.1mol (16.3g) γ-aminopropyltriethoxy dimethoxysilane is added in 0.1L deionized water, then the 0.1L aqueous solution being dissolved with 0.1mol (9.8g) phosphoric acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain water white sol solution, or steam again desolventize after the solid of yellow transparent.
Embodiment 17
At normal temperatures, first 0.1mol (17.9g) γ-aminopropyltrimethoxysilane and 0.1mol (19.1g) γ-aminopropyltriethoxy diethoxy silane are added in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.2mol (6.6g) Hypophosporous Acid, 50 is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 4 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 18
At normal temperatures, first by 0.3mol (53.8g) γ-aminopropyltrimethoxysilane with 0.2mol (44.5g) γ-(quadrol base) propyl trimethoxy silicane adds in 0.3L deionized water, then the solution being dissolved with the 0.1L second alcohol and water of 0.1mol (23.2g) DOPO-OH is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 12 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 19
At normal temperatures, first by 0.1mol (22.1g) γ-aminopropyl triethoxysilane with 0.1mol (22.2g) γ-(quadrol base) propyl trimethoxy silicane adds in 0.3L deionized water, then the 0.1L aqueous solution being dissolved with 0.1mol (8.2g) phosphorous acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 20
At normal temperatures, first by 0.2mol (44.2g) γ-aminopropyl triethoxysilane with 0.1mol (20.6g) γ-(quadrol base) hydroxypropyl methyl dimethoxysilane adds in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.1mol (14.2g) phenyl Hypophosporous Acid, 50 is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 5 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 21
At normal temperatures, first by 0.1mol (22.2g) γ-(quadrol base) propyl trimethoxy silicane with 0.1mol (23.2g) γ-(quadrol base) hydroxypropyl methyl diethoxy silane adds in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.1mol (21.4g) phenyl-phosphonic acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 8 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 22
At normal temperatures, first 0.2mol (38.3g) γ-aminopropyltriethoxy diethoxy silane and 0.1mol (26.5g) diethylenetriamine base propyl trimethoxy silicane are added in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.1mol (21.4g) CEPPA is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 23
At normal temperatures, first 0.1mol (19.1g) γ-aminopropyltriethoxy diethoxy silane and 0.1mol (30.5g) diethylenetriamine base propyl-triethoxysilicane are added in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.3mol (19.8g) Hypophosporous Acid, 50 is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 24
At normal temperatures, first 0.1mol (19.1g) γ-aminopropyltriethoxy diethoxy silane and 0.1mol (30.5g) diethylenetriamine base propyl-triethoxysilicane are added in 0.2L deionized water, then the solution being dissolved with the 0.1L second alcohol and water of 0.2mol (46.4g) DOPO-OH is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 25
At normal temperatures, first 0.1mol (22.2g) γ-(quadrol base) propyl trimethoxy silicane and 0.1mol (16.3g) γ-aminopropyltriethoxy dimethoxysilane are added in 0.2L deionized water, then the solution being dissolved with the 0.1L second alcohol and water of 0.2mol (43.6g) diphenyl phosphonic acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 12 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 26
At normal temperatures, first by 0.1mol (22.2g) γ-(quadrol base) propyl trimethoxy silicane with 0.1mol (23.2g) γ-(quadrol base) hydroxypropyl methyl diethoxy silane adds in 0.2L deionized water, then the solution being dissolved with the 0.1L second alcohol and water of 0.1mol (6.6g) Hypophosporous Acid, 50 and 0.1mol (23.2g) DOPO-OH is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 10 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 27
At normal temperatures, first by 0.2mol (44.2g) γ-aminopropyl triethoxysilane with 0.1mol (22.2g) γ-(quadrol base) propyl trimethoxy silicane adds in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.1mol (6.6g) Hypophosporous Acid, 50 and 0.1mol (8.2g) phosphorous acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 28
At normal temperatures, first 0.2mol (44.4g) γ-(quadrol base) propyl trimethoxy silicane and 0.2mol (32.6g) γ-aminopropyltriethoxy dimethoxysilane are added in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.1mol (6.6g) Hypophosporous Acid, 50,0.1mol (14.2g) phenyl Hypophosporous Acid, 50 and 0.1mol (8.2g) phosphorous acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 6 hours, obtain water white sol solution, or again steam desolventize after water white solid.
Embodiment 29
At normal temperatures, first by 0.1mol (22.2g) γ-(quadrol base) propyl trimethoxy silicane, 0.1mol (23.2g) γ-(quadrol base) hydroxypropyl methyl diethoxy silane and 0.1mol (22.2g) γ-(quadrol base) propyl trimethoxy silicane adds in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.2mol (19.6g) phosphoric acid is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 8 hours, obtain the sol solution of pale yellow transparent, or steam again desolventize after the solid of yellow transparent.
Embodiment 30
At normal temperatures, first by 0.1mol (22.2g) γ-(quadrol base) propyl trimethoxy silicane, 0.1mol (23.2g) γ-(quadrol base) hydroxypropyl methyl diethoxy silane and 0.1mol (22.2g) γ-(quadrol base) propyl trimethoxy silicane adds in 0.2L deionized water, then the 0.1L aqueous solution being dissolved with 0.1mol (6.6g) Hypophosporous Acid, 50 and 0.1mol (21.4g) CEPPA is dripped while stirring, drip rear continuation at normal temperatures stirring reaction within 8 hours, obtain the sol solution of pale yellow transparent, or steaming obtains the solid of yellow transparent after desolventizing again.
In order to investigate the flame retardant effect of water-based halogen-free fire retardant prepared by the present invention, the aqueous fire retardant that above section Example is prepared by the present invention is applied in resistance combustion polyurethane foam, epoxy resin, polyolefine wood-plastic mixture and polyvinyl alcohol as flame-retardant additive, and it can be used as fire-retardant treatment liquid to be applied in flame-retardant textile, timber and paper, and test the limiting oxygen index(LOI) of these materials before and after fire retardant process provided by the invention and vertical combustion grade.
Application examples 1
Should use-case be that the water-based halogen-free fire retardant of gained in embodiment 10 is added in the flexible PU foam prepared with single stage method foam process, its raw materials used formula is as following table, the limiting oxygen index(LOI) of gained flexible PU foam is 22.5%, and can pass through CalT.B.117A testing standard.
Application examples 2
Should use-case be that the water-based halogen-free fire retardant of gained in embodiment 10 is added in the flexible PU foam prepared with single stage method foam process, its raw materials used formula is as following table, the limiting oxygen index(LOI) of gained flexible PU foam is 23.5%, and can pass through CalT.B.117A testing standard.
Application examples 3
Should use-case be that the water-based halogen-free fire retardant of gained in embodiment 10 is added in the flexible PU foam prepared with single stage method foam process, its raw materials used formula is as following table, the limiting oxygen index(LOI) of gained flexible PU foam is 24.5%, and can pass through CalT.B.117A testing standard.
Application examples 4
Should use-case be that the water-based halogen-free fire retardant of gained in embodiment 13 is added in the flexible PU foam prepared with single stage method foam process, its raw materials used formula is as following table, the limiting oxygen index(LOI) of gained flexible PU foam is 23.0%, and can pass through CalT.B.117A testing standard.
Application examples 5
Should use-case be that the water-based halogen-free fire retardant of gained in embodiment 5 is added in the hard polyurethane foams prepared with single stage method foam process, its raw materials used formula is as following table, the limiting oxygen index(LOI) of gained flexible PU foam is 23.0%, and vertical combustion grade is stepless.
Application examples 6
Should use-case be that the water-based halogen-free fire retardant of gained in embodiment 5 is added in the hard polyurethane foams prepared with single stage method foam process, its raw materials used formula is as following table, the limiting oxygen index(LOI) of gained flexible PU foam is 25.5%, and vertical combustion grade is V-0.
Application examples 7
Should use-case be that the water-based halogen-free fire retardant of gained in embodiment 5 is added in the hard polyurethane foams prepared with single stage method foam process, its raw materials used formula is as following table, the limiting oxygen index(LOI) of gained flexible PU foam is 26.5%, and vertical combustion grade is V-0.
Application examples 8
Should use-case be that the water-based halogen-free fire retardant of gained in embodiment 15 is added in the hard polyurethane foams prepared with single stage method foam process, its raw materials used formula is as following table, the limiting oxygen index(LOI) of gained flexible PU foam is 27.5%, and vertical combustion grade is V-0.
Application examples 9
Should use-case be by the water-based halogen-free fire retardant 1 part of gained in embodiment 1, be added in 10 parts of polyurethane slurries under high velocity agitation, and in its Teflon mould poured into, solvent spontaneous evaporation is made in fluidizing air, the limiting oxygen index(LOI) of gained use for synthetic leather polyurethane slurry is 27.0%, and vertical combustion grade is V-0.
Application examples 10
Should use-case be by the water-based halogen-free fire retardant 1 part of gained in embodiment 5, be added in 10 parts of polyurethane slurries under high velocity agitation, and in its Teflon mould poured into, solvent spontaneous evaporation is made in fluidizing air, the limiting oxygen index(LOI) of gained use for synthetic leather polyurethane slurry is 28.5%, and vertical combustion grade is V-0.
Application examples 11
First by the water-based halogen-free fire retardant 1 part of embodiment 2 gained and epoxy prepolymer 19 parts of premix mixings, then with at 80-120 DEG C solidify 2-3h.The limiting oxygen index(LOI) of this fire retarding epoxide resin is 25.5%, and vertical combustion grade is V-1.
Application examples 12
First by the water-based halogen-free fire retardant 2 parts of embodiment 2 gained and epoxy prepolymer 18 parts of premix mixings, then with at 80-120 DEG C solidify 2-3h.The limiting oxygen index(LOI) of this fire retarding epoxide resin is 27.5%, and vertical combustion grade is V-0.
Application examples 13
First by the water-based halogen-free fire retardant 1 part of embodiment 3 gained and epoxy prepolymer 19 parts of premix mixings, then with at 80-120 DEG C solidify 2-3h.The limiting oxygen index(LOI) of this fire retarding epoxide resin is 28.5%, and vertical combustion grade is V-0.
Application examples 14
First by the water-based halogen-free fire retardant 2 parts of embodiment 3 gained and epoxy prepolymer 18 parts of premix mixings, then with at 80-120 DEG C solidify 2-3h.The limiting oxygen index(LOI) of this fire retarding epoxide resin is 31.5%, and vertical combustion grade is V-0.
Application examples 15
First by even to the water-based halogen-free fire retardant 10 parts of embodiment 1 gained, 45 parts of wood powders and 45 parts of polyethylene premixs, then put into Banbury mixer melting and mix shaping with rear fender.The limiting oxygen index(LOI) of this flame-proof polyethylene wood plastics composite thing is 22.5%, and vertical combustion grade is stepless.
Application examples 16
First by even to the water-based halogen-free fire retardant 15 parts of embodiment 1 gained, 42.5 parts of wood powders and 42.5 parts of polyethylene premixs, then put into Banbury mixer melting and mix shaping with rear fender.The limiting oxygen index(LOI) of this flame-proof polyethylene wood plastics composite thing is 24.5%, and vertical combustion grade is V-1.
Application examples 17
First by even to the water-based halogen-free fire retardant 20 parts of embodiment 1 gained, 40.0 parts of wood powders and 40.0 parts of polyethylene premixs, then put into Banbury mixer melting and mix shaping with rear fender.The limiting oxygen index(LOI) of this flame-proof polyethylene wood plastics composite thing is 27.0%, and vertical combustion grade is V-0.
Application examples 18
First by even to the water-based halogen-free fire retardant 20 parts of embodiment 17 gained, 40 parts of wood powders and 40 parts of polypropylene premixs, then put into Banbury mixer melting and mix shaping with rear fender.The limiting oxygen index(LOI) of this polypropylene flame redardant wood plastics composite thing is 26.5%, and vertical combustion grade is V-0.
Application examples 19
First by even to the water-based halogen-free fire retardant 20 parts of embodiment 23 gained, 40 parts of wood powders and 40 parts of polypropylene premixs, then put into Banbury mixer melting and mix shaping with rear fender.The limiting oxygen index(LOI) of this polypropylene flame redardant wood plastics composite thing is 28.0%, and vertical combustion grade is V-0.
Application examples 20
First the water-based halogen-free fire retardant 1.5 parts of embodiment 17 gained and polyvinyl alcohol 8.5 parts are put into 100 parts of deionized waters, at 95 DEG C, strong stirring backflow obtains water white solution, and then to pour in corresponding glass mold Air drying several weeks into.The limiting oxygen index(LOI) of this anti-flaming polyvinyl alcohol is 26.5%, and vertical combustion grade is V-0.
Application examples 21
First the water-based halogen-free fire retardant 1 part of embodiment 17 gained, polynite 0.5 part and polyvinyl alcohol 8.5 parts are put into 100 parts of deionized waters, at 95 DEG C, strong stirring backflow obtains light brown translucent solution, and then to pour in corresponding glass mold Air drying several weeks into.The limiting oxygen index(LOI) of this anti-flaming polyvinyl alcohol is 28.5%, and vertical combustion grade is V-0.
Application examples 22
First the water-based halogen-free fire retardant 1.0 parts of embodiment 19 gained, polynite 0.5 part and polyvinyl alcohol 8.5 parts are put into 100 parts of deionized waters, at 95 DEG C, strong stirring backflow obtains light brown translucent solution, and then to pour in corresponding glass mold Air drying several weeks into.The limiting oxygen index(LOI) of this anti-flaming polyvinyl alcohol is 27.0%, and vertical combustion grade is V-0.
Application examples 23
First the water-based halogen-free fire retardant 1.0 parts of embodiment 29 gained, polynite 0.5 part and polyvinyl alcohol 8.5 parts are put into 100 parts of deionized waters, at 95 DEG C, strong stirring backflow obtains light brown translucent solution, and then to pour in corresponding glass mold Air drying several weeks into.The limiting oxygen index(LOI) of this anti-flaming polyvinyl alcohol is 29.0%, and vertical combustion grade is V-0.
Application examples 24
By the waterborne flame retardant agent solution after dilution of gained in embodiment 5, utilize the technique that dipping is dried, obtain the flame retardant modification cotton fabric that fire retardant charge capacity is 5.5%, its limiting oxygen index(LOI) is 24.5%, and vertical combustion grade is stepless.
Application examples 25
By the waterborne flame retardant agent solution after dilution of gained in embodiment 5, utilize the technique that dipping is dried, obtain the flame retardant modification cotton fabric that fire retardant charge capacity is 9.6%, its limiting oxygen index(LOI) is 30.5%, vertical combustion grade V-0.
Application examples 26
By the waterborne flame retardant agent solution after dilution of gained in embodiment 5, utilize the technique that dipping is dried, obtain the flame retardant modification cotton fabric that fire retardant charge capacity is 14.3%, its limiting oxygen index(LOI) is 34.5%, vertical combustion grade V-0.
Application examples 27
By the waterborne flame retardant agent solution after dilution of gained in embodiment 23, utilize the technique that dipping is dried, obtain the flame retardant modification cotton fabric that fire retardant charge capacity is 10.8%, its limiting oxygen index(LOI) is 33.5%, vertical combustion grade V-0.
Application examples 28
By the waterborne flame retardant agent solution after dilution of gained in embodiment 16, utilize the technique that dipping is dried, obtain the flame-retardant modified polyester piece good that fire retardant charge capacity is 5.8%, its limiting oxygen index(LOI) is 24.5%, and vertical combustion grade is stepless, without molten drop.
Application examples 29
By the waterborne flame retardant agent solution after dilution of gained in embodiment 16, utilize the technique that dipping is dried, obtain the flame-retardant modified polyester piece good that fire retardant charge capacity is 10.4%, its limiting oxygen index(LOI) is 27.5%, and vertical combustion grade V-0, without molten drop.
Application examples 30
By the waterborne flame retardant agent solution after dilution of gained in embodiment 16, utilize the technique that dipping is dried, obtain the flame-retardant modified polyester piece good that fire retardant charge capacity is 14.8%, its limiting oxygen index(LOI) is 29.0%, and vertical combustion grade V-0, without molten drop.
Application examples 31
By the waterborne flame retardant agent solution after dilution of gained in embodiment 4, utilize the technique that dipping is dried, obtain the flame-retardant modified polyester piece good that fire retardant charge capacity is 5.6%, its limiting oxygen index(LOI) is 32.5%, and vertical combustion grade V-0 has a small amount of molten drop.
Application examples 32
By the waterborne flame retardant agent solution after dilution of gained in embodiment 4, utilize the technique that dipping is dried, obtain the flame-retardant modified polyester piece good that fire retardant charge capacity is 9.6%, its limiting oxygen index(LOI) is 36.5%, and vertical combustion grade V-0 has a small amount of molten drop.
Application examples 33
By the waterborne flame retardant agent solution after dilution of gained in embodiment 3, utilize the technique that dipping is dried, obtain the flame-retardant modified polyester-cotton blend 80/20 that fire retardant charge capacity is 8.9%, its limiting oxygen index(LOI) is 24.5%, horizontal firing grade HB.
Application examples 34
By the waterborne flame retardant agent solution after dilution of gained in embodiment 5, utilize the technique that dipping is dried, obtain the flame-retardant modified polyester-cotton blend 80/20 that fire retardant charge capacity is 10.5%, its limiting oxygen index(LOI) is 24.0%, horizontal firing grade HB.
Application examples 35
By the waterborne flame retardant agent solution after dilution of gained in embodiment 5, utilize the technique that dipping is dried, obtain the flame-retardant modified paper that fire retardant charge capacity is 5.6%, its limiting oxygen index(LOI) is 27.0%, vertical combustion carbonization value 87mm.
Application examples 36
By the waterborne flame retardant agent solution after dilution of gained in embodiment 5, utilize the technique that dipping is dried, obtain the flame-retardant modified paper that fire retardant charge capacity is 9.3%, its limiting oxygen index(LOI) is 30.0%, vertical combustion carbonization value 73mm.
Application examples 37
By the waterborne flame retardant agent solution after dilution of gained in embodiment 24, utilize the technique that dipping is dried, obtain the flame-retardant modified paper that fire retardant charge capacity is 10.2%, its limiting oxygen index(LOI) is 32.5%, vertical combustion carbonization value 65mm.
Application examples 38
By the waterborne flame retardant agent solution of gained in embodiment 3, the technique utilizing dipping to dry, obtain the flame-retardant wood board that fire retardant weightening finish is 5.3%, its limiting oxygen index(LOI) is 27.0%.
Application examples 39
By the waterborne flame retardant agent solution of gained in embodiment 3, the technique utilizing dipping to dry, obtain the flame-retardant wood board that fire retardant weightening finish is 9.3%, its limiting oxygen index(LOI) is 32.5%
Application examples 40
By the waterborne flame retardant agent solution of gained in embodiment 8, the technique utilizing dipping to dry, obtain the flame-retardant wood board that fire retardant weightening finish is 9.8%, its limiting oxygen index(LOI) is 36.5%.
Comparative example 1
Utilize the flexible PU foam of single stage method foaming preparation, its limiting oxygen index(LOI) is 18.0%, not by Cal.T.B.117A standard.Single stage method foams formula used as following table:
Comparative example 2
Utilize the flexible PU foam of single stage method foaming preparation, its limiting oxygen index(LOI) is 19.0%, and vertical combustion grade is stepless.Single stage method foams formula used as following table:
Comparative example 3
Be poured in Teflon mould by 10g polyurethane slurry under high velocity agitation, make solvent spontaneous evaporation in fluidizing air, the limiting oxygen index(LOI) of gained use for synthetic leather polyurethane slurry is 21.5%, and vertical combustion grade is stepless.
Comparative example 4
By diethylenetriamine 1 part and epoxy prepolymer 19 parts mixing, then solidify 2-5h at normal temperatures.The limiting oxygen index(LOI) of this fire retarding epoxide resin is 20.5%, and vertical combustion grade is V-0.
Comparative example 5
First by 50.0 parts of wood powders and 50.0 parts of polyethylene premixs even, it is shaping with rear fender then to put into Banbury mixer melting mixing.The limiting oxygen index(LOI) that mixture moulded by this flame-proof polyethylene wood is 19.5%, and vertical combustion grade is stepless.
Comparative example 6
First by 50.0 parts of wood powders and 50.0 parts of polypropylene premixs even, it is shaping with rear fender then to put into Banbury mixer melting mixing.The limiting oxygen index(LOI) that mixture moulded by this polypropylene flame redardant wood is 19.5%, and vertical combustion grade is stepless.
Comparative example 7
Without fire retardant cotton fabric before treatment, its limiting oxygen index(LOI) is 19.0%, and vertical combustion grade is stepless.
Comparative example 8
Without fire retardant woven dacron before treatment, its limiting oxygen index(LOI) is 21.0%, and vertical combustion grade is stepless.
Comparative example 9
Without fire retardant polyester-cotton blend 80/20 before treatment, its limiting oxygen index(LOI) is 18.0%, and horizontal firing grade is stepless.
Comparative example 10
Without fire retardant paper before treatment, its limiting oxygen index(LOI) is 19.5%, and vertical combustion is damaged completely.
Comparative example 11
Without fire retardant timber before treatment, its limiting oxygen index(LOI) is 20.0%.

Claims (8)

1. a water-based halogen-free fire retardant, is characterized in that this fire retardant is at least one in following general structure:
R in formula is CH 3, OCH 3, OC 2h 5or OH, x and y be more than or equal to 0 but be asynchronously 0 integer, m and n is 0,1 or 2, can identical also can not be identical, 0 < a≤(m+1) x+ (n+1) y.
2. prepare the method for water-based halogen-free fire retardant according to claim 1 for one kind, it is characterized in that the method is at normal temperatures, first Amol amino silicane coupling agent is added in excessive water, then the phosphorous water of acid of Bmol or the solution of second alcohol and water is dripped while stirring, namely drip off rear continuation stirring reaction obtains colourless to flaxen transparent liquid after 2-12 hour, or steaming obtains colourless to yellow transparent solid or thick liquid, wherein 0 < B≤3A after desolventizing again.
3. the preparation method of water-based halogen-free fire retardant according to claim 2, is characterized in that A and the B described in the method is A:B=1-2:1.
4. the preparation method of the water-based halogen-free fire retardant according to Claims 2 or 3, it is characterized in that amino silicane coupling agent described in the method is γ-aminopropyltrimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, γ-(quadrol base) propyl trimethoxy silicane, γ (-quadrol base) propyl-triethoxysilicane, γ-(quadrol base) hydroxypropyl methyl dimethoxysilane, γ (-quadrol base) hydroxypropyl methyl diethoxy silane, diethylenetriamine base propyl trimethoxy silicane, diethylenetriamine base propyl-triethoxysilicane, at least one in γ-(diethylenetriamine base) hydroxypropyl methyl dimethoxysilane and γ-(diethylenetriamine base) hydroxypropyl methyl diethoxy silane.
5. the preparation method of the water-based halogen-free fire retardant according to Claims 2 or 3, it is characterized in that acid phosphorous described in the method is at least one in Hypophosporous Acid, 50, phenyl phosphinic acid, diphenyl phosphonic acid, 10-hydroxyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorous acid, phenyl-phosphonic acid and 2-carboxyethyl phenyl Hypophosporous Acid, 50 or phosphoric acid.
6. the preparation method of water-based halogen-free fire retardant according to claim 4, it is characterized in that acid phosphorous described in the method is at least one in Hypophosporous Acid, 50, phenyl phosphinic acid, diphenyl phosphonic acid, 10-hydroxyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorous acid, phenyl-phosphonic acid and 2-carboxyethyl phenyl Hypophosporous Acid, 50 or phosphoric acid.
7. the application of a water-based halogen-free fire retardant according to claim 1 in flame retarded polymeric material.
8. the application of a water-based halogen-free fire retardant according to claim 1 in flame-retardant textile, timber or paper.
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CN108189183B (en) * 2017-07-27 2019-07-26 北京希凯科技有限公司 A kind of wooden cultural relic ancient architecture long-acting fire-retardant combination and its flame-proof treatment method
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CN112266481A (en) * 2020-10-27 2021-01-26 中国林业科学研究院林产化学工业研究所 Maleopimaric acid modified silicon-phosphorus synergistic flame retardant, preparation method thereof and flame-retardant polyurethane foam prepared from maleopimaric acid modified silicon-phosphorus synergistic flame retardant

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