CN108314899A - A kind of nano-meter flame retardants preparation method - Google Patents
A kind of nano-meter flame retardants preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/398—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing boron or metal atoms
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Abstract
The present invention provides a kind of nano-meter flame retardants preparation method, first mixes boric acid with end hydroxyl silicone oil and small molecule siloxanes in proportion, and heating is allowed to dissolve.Then so that small-molecule substance is loaded into modified halloysite nanotubes cavity with negative pressure by milling, obtains the halloysite nanotubes of load small-molecule substance.Then cross-linking reaction, generation load the halloysite nanotubes of poly- boric acid silicone oil ester under concentrated sulfuric acid catalyst.It is finally reacted under certain condition with above-mentioned product with phosphorus oxychloride, obtains the halloysite nanotubes for loading poly- phosphorus Borosiloxane, i.e. nano-meter flame retardants.For the present invention compared with conventional flame retardant, the preparation method technological process is simple, is swift in response, and reaction efficiency is high, product yield high.Meanwhile by adjusting synthesis and preparation process, optimizes three kinds of its phosphorus, boron, silicon element compositions, can have notable flame retardant effect.
Description
Technical field
The invention belongs to high molecular material flame retardant areas, and in particular to a kind of nano-meter flame retardants preparation process.
Background technology
The fire retardant of the existing development and production in China is generally in the low side raw material stage, with low content of technology, though yield is big,
The output value is low, profit margin very little, lacks the competitive advantage in international market.It also cannot be satisfied some special materials, high-performance simultaneously
The fire-retardant demand of material.Main problem existing for existing flame retardant products is that flame retardant effect is poor, and additive amount is big and seriously affects material
The comprehensive performance of material, mostly based on poisonous and hazardous halogenated flame retardant product；Lack the research to novel flame-retardant mechanism and resistance
Fire new product research；Some flame retardant products newly developed due to complex process, production cost is high and is difficult to large-scale promotion.With
The developed countries such as European Union increase substantially material flame-retardant standard, and China's fire retardant industry will reshuffle, the existing resistance of the overwhelming majority
Firing agent product will be on the verge of being replaced.
Currently used fire retardant includes several classes such as organic halogen system, organic phosphorus and inorganic combustion inhibitor.Halogenated flame retardant
It is the mainstream product in flame retardant area from the 1960s, flame retarding efficiency is high, and dosage is few, to the performance of material
It influences small and moderate.1986, research found that halogenated flame retardant forms dioxin in application process, serious to poison
Environment, along with generating a large amount of flue dust and corrosive gas, mesh in thermal cracking and burning with its fire-retardant high molecular material
Preceding halogenated flame retardant is on the verge of being replaced by limitation use in developed country.
Phosphorus flame retardant is also a type, including phosphate, phosphate, phosphonitrile etc. important in conventional flame retardant,
Middle phosphate species are more, price is low, purposes is wider, are principal item.The organic phosphorus flame retardant of early development application has phosphoric acid
Triphenylmethyl methacrylate, tricresyl phosphate（Dimethylbenzene）Ester, triethyl phosphate, phosphoric acid tri-isopropyl benzene ester, trioctyl phosphate, tolyl diphenyl phosphonic acid
Ester, tricresyl phosphate（β-chloroethyl）Ester, tricresyl phosphate（2,3- dibromopropyls）Ester, three（Dibromo phenyl）Phosphate etc..Phosphate ester product
Mostly liquid, poor heat resistance, volatility is big, affects flame retardant effect and fire-retardant persistence.Phosphorus halogen system composite flame-retardant agent is also because of it
The problems such as halogen, using being restricted.Therefore, volatility is low, and heat resistance is good and fire-retardant lasting novel environment friendly organophosphor
The research and development of fire retardant are increasingly becoming the hot spot studied at present.Lina synthesizes phosphorous-containing polyester by phenylphosphonyl dichloride and sweet glycol
PEDPP, adds the PEDPP of 10wt% in high polymer, and LOI reaches 29.In addition, phosphorous dissaving polymer is as fire-retardant
Agent new varieties also obtain extensive concern.Xilei Chen have synthesized a kind of hyperbranched polyphosphate（HPE）And it is added to
Melt blending in polymer finds linearly increasing, the addition of 20wt% with the increase of HPE additive amounts of flame retardance of polymer performance
Amount can make blend pass through UL94 V-0 level estimates, and LOI reaches 35.It is other to also have the bis- diphenyl phosphoesters of such as bisphenol-A-
（BDP）It is double with resorcinol（Diphenyl）Phosphate（ RDP）It is that the New-type halide-free environmental protection organic phosphates developed in recent years are fire-retardant
Agent；Novel bicyclic young laying ducks in cage tripolymer；The annular phosphonate of serial special construction（PBPP、TEMP P-oxide、TEMP
PP'-dioxide）；And the series such as phosphorus azepine mould assembly, phosphorus sila mould assembly.
Though being developed and reporting there are many novel phosphorus flame retardant at present, not yet enter industrialized production and application neck
Domain.Especially phosphonium flame retardant preparation process is complicated, and production cost is high, it is difficult to industrialize.Compared with halogenated flame retardant, some phosphorus
Flame retardant can't be equal to therewith in efficiency and price.Therefore, solving the problems, such as phosphorus flame retardant, presently, there are need to also be into
One step effort.
Silicon-series five-retardant is the up-and-coming youngster in fire-retardant family, its exploitation is later than halogen system and phosphorus flame retardant, but it with
Its outstanding anti-flammability, low burning rate, low heat release, anti-drip, good processability, high fluidity are especially environmentally friendly, low
Cigarette, low CO production quantity and be concerned.But the poor compatibility of simple silicon-series five-retardant and high molecular material, and valence
Lattice are higher.When phosphorous, Silicone-containing Flame Retardant is used in conjunction with, P elements can be catalyzed the formation for facilitating charcoal under high temperature, and element silicon then increases
Flame retarding efficiency can be improved to play phosphorus-silicon cooperative flame retardant effect in the thermal stability for adding these layer of charcoal, reduces application cost.
Chinese document《Fine-chemical intermediate》The 4th phase of volume 40：Organophosphorous fire retardant New research progress is mentioned 2004
Peng Zhihan etc. reports a kind of siliceous phosphonate fire retardant SPFA for pure cotton fabric flame retardant treatment of structure novel, this silicon phosphorus
Flame retardant can improve the charring rate of material.Zhang in 2006 etc. has using silica and pentaerythrite as Material synthesis
The caged bicyclic phosphates fire retardant CPQS of symmetrical structure, heat analysis the result shows that, caged bicyclic phosphates are at 700 DEG C
Weightlessness is only 19.98%, and layer of charcoal is in closely knit sheet, is applied in epoxy resin, 20% additive amount can be such that LOI values reach
To 26.5, and realize UL94 V-0 detections, the thermal stability of resin also increases.Ding in 2009 etc. has synthesized structure pair
The phosphorous of title, silicon fire retardant DOPO-TMDS and DOPO-DMDP are simultaneously applied in epoxy resin, the results showed that the two contains
Phosphorus silicon fire retardant is all significantly increased to the thermal stability of resin, mechanical performance and flame retardant property, especially flame retardant property, when
When phosphorus content is 2% in resin, LOI values can reach 32-33, and vertical combustion realizes V-0 grades.Hu in 2010 etc. is with DOPO and ethylene
Triethoxysilane is Material synthesis P（DOPO-VTES）, thermal weight loss display P（DOPO-VTES）It is high in 700 DEG C of carbon yields
Up to 86.31%, it is applied in makrolon when additive amount is 5%, LOI values are up to 32.8, when adding 2% montmorillonite,
Vertical combustion reaches V-0 grades.
In recent years, inorganic nano fire proofing is after conventional metals chemical combination species aluminium hydroxide, magnesium hydroxide, boride, calcium
Research vision is reentered after compound, iron compound, antimonial, and is rapidly developed.Its notable advantage be it is nontoxic,
Easy addition, using flexible, it is cheap, be easy to be prepared on a large scale, nature reserves are enriched.The disadvantage is that require additive amount big,
Difficulties in dispersion in the polymeric material is affected to material body performance.Current research trends mainly realize micronizing
Or even the surface treatment of nanosizing, particulate matter, the compounded technology etc. with other fire retardants.Main nano-particle includes layer
Shape silicate（MMT）, polyhedral oligomeric silsesquioxane (POSS), nano silicon dioxide, carbon nanotube, sepiolite, expanded graphite,
Graphene etc..
Height in 2010 builds the reports such as honor, nano imvite and haplotype fire retardant (such as ammonium polyphosphate, melamine) or
The common modified polypropene of composite flame retardant system, nylon 6, epoxy resin and polyurethane etc. are found in polymer/montmorillnoite nano
Conventional flame retardant is added in composite material in the case where not reducing fire-retardant rank, the dosage of fire retardant is (with pure Polymers Phase
Than) significantly reduce.It can be seen that organic fire-retardant and nano imvite have cooperative flame retardant effect.But since this compounding is only simple
Physical mixed, therefore the cooperative flame retardant effect of the two is fairly limited, can be with having in order to more preferably play this synergistic effect
Machine phosphorus compound nitrogen series carry out organic-treating to nano imvite and carry out synthesizing new composite flame-retardant agent.
Feng Yang in 2011 and Gordon L.Nelson report nano silicon dioxides and attapulgite clay and a kind of board
Number be SINK polysiloxanes, borate composite flame-retardant agent（Additive amount 20%）Collaboration is in use, have polystyrene material non-
Normal significant flame retardant effect, heat release rate peak value（PHRR）530 are reduced to from the 1212 of simple polystyrene, is decreased by
56%。
Liqiang Zhang, Meng Zhang, Yonghong Zhou, Lihong Hu application expanded graphites in 2013
With triethyl phosphate as composite flame-retardant agent, its flame retardant effect to polyurethane foamed material is evaluated, LOI values can reach
29.7%, PHRR can reach 127.78kW/m2。
Refined wait of Ran Shi in 2013 is modified montmorillonite using acid-alkali treatment method, then the montmorillonite that soda acid is handled and phosphorus
Ester flame-proof agent compounds, as the fire-retardant of polycarbonate/acrylonitrile-butadiene-styrene terpolymer (PC/ABS) alloy
System, and characterize thermal stability and flame retardant property of the soda acid processing montmorillonite to alloy.The result shows that resorcinol bis- (two
Phenyl phosphate ester) modified montmorillonite (BDP-MMT) makes the initial decomposition temperature of fire retardation PC/ABS alloy reduce, and at soda acid
Reason montmorillonite but makes the initial decomposition temperature of alloy increase；The addition of BDP-MMT can deteriorate the barrier property of carbon-coating, and sour
Alkali process montmorillonite can but increase the stability of carbon-coating, the time delay for making the second peak heat release occur, and suitable acid
Concentration processing montmorillonite can make the high molecule alloy material pass through UL-94 V-0 level testings.
2014, TaoYu, NingJiang, YanLi gave to the world the result of one's studies, by 9,10-dihydro-9-oxa-10-
Phosphaphenanthrene-10-oxide (DOPO) is bonded on multi-walled carbon nanotube, and 5% additive amount can make its LOI value
It is increased to 26.4%, passes through UL-94 V-0 level testings.
2015 Nian Zhao Yue etc. will be added to thermoplasticity after hypo-aluminum orthophosphate (AHP) and melamine cyanurate (MCA) compounding
Fire-retardant TPU materials are prepared in polyurethane (TPU), passes through oxygen index (OI) (OI) and vertical combustion (UL-94) testing research material
Flame retardant property determines the thermal stability and carbon-forming performance of material by thermogravimetric analysis (TGA) technology, while being investigated AHP
Influence of the mass ratio different from MCA to TPU material properties.The result shows that：When the mass ratio of AHP and MCA is 1:2, fire retardant
Total addition level be 11% when, fire-retardant TPU materials can be V-0 grades by vertical combustion UL-94, and OI has reached 25.2%.TGA is tested
The result shows that：The addition of fire retardant AHP/MCA does not influence the starting heat decomposition temperature of TPU materials, but can improve material and exist
Thermal stability when high temperature, while improving the carbon-forming performance of material.Increased layer of charcoal can effectively stop oxygen and heat enters
To material internal, inhibit the effusion of internal imflammable gas, while AHP and MCA can release fire retardant gas, dilution oxygen and can
The concentration of combustion property gas, to improve the flame retardant property of material.
Hu in 2015 waits quietly carrying out pressurization closed oxidation processes to expansible graphite using improved Hummers methods, prepares
Graphene oxide (GO), has studied GO contents to GO/ aqueous polyurethanes（WPU）Stability, form, the heat of nanocomposite
The influence of degradation property and flame retardant property.The carbon left of the GO nano composite systems of content 2% is increased to from 0.99% at 800 DEG C
2.90%.Cone calorimetry analysis result shows that the content with GO in GO/WPU nanocomposites increases, the resistance of material
Combustion smoke suppressing gradually increases.It is compared with pure WPU when the content of GO is 2%, the peak heat of GO/WPU nanocomposites is released
Put rate, total release heat, the release of total cigarette and the cigarette factor reduces 34%, 19%, 27% and 43% respectively.
SherifElbasuney in 2015 reports that a kind of application supercritical water hydro-thermal method continuously synthesizes AlOOH rod-like nanos
The new technology of particle, and as fire retardant application.AlOOH explains amplification quantity hydrone, 550 DEG C of endothermic decompositions in 223 DEG C of time-divisions
Form Al2O3, there is good flame retardant effect.Sherif Elbasuney have also synthesized a kind of Mg6Al2(CO3)(OH)16•4H2O's
Layered double-hydroxide（LDH）, with the up to heat absorption capacity of 478.6 J/g at 354 DEG C.
Developed country including European Union is actively promoting formulation and the legislation work of fire proofing new standard in recent years
Make, such as in March, 2013, European Union have passed through one about train interior trimming material and the new standard of composition safety：EN 45545-2：
2013 " rail vehicle flameproof protection part 2s：The fire protection requirement of material and element ".The standard introduces very stringent easy
Combustion property test method and performance requirement.Therefore, additive amount is small, flame retardant effect new flame retardant gesture outstanding is must for research and development
Row.
Invention content
To solve the disadvantage that the prior art and deficiency, it is an object of the present invention to provide a kind of nano-meter flame retardants, i.e. nanosizing angstrom
Lip river stone/poly- phosphorus Borosiloxane fire retardant.
Principle explanation：The flame retardant materials, using halloysite nanotubes as nano-carrier, three kinds of load phosphorus, boron, silicon elements
The poly- phosphorus Borosiloxane of hydridization is hindered by controlling the reaction ratio of three kinds of elements with obtaining the nanometer with preferable flame retardant effect
Fire agent powder.
According to fire-retardant theoretical and fire retardant development and application experience, targeted design novel flame-retardant molecular structure and production
Product feature, using flame-retardant polymer, inorganic matter nanocomposite as research direction, in conjunction with the MOLECULE DESIGN of organo-silicon compound,
Boracic, phosphorus-containing groups are introduced, poly- phosphorus Borosiloxane high-crosslinking-degree polymer is synthesized.The polymer is by three kinds of phosphorus, boron, silicon fire-retardant members
Element is introduced into same molecule segment, advantageously forms flame retardant synergistic effect, significantly improve organic silicon fibre retardant flame retardant property,
Base material processing performance and mechanical property and composite material high temperature resistant and oxidation resistance.
Using the lar nanometric cavities structure of halloysite nanotubes, the embedding to poly- phosphorus Borosiloxane flame-retardant composition and nanometer are realized
Change.The crosslinking behavior of organic siliconresin and inorganic silicon nano material, poly- phosphorus Borosiloxane composite flame-retardant agent are studied in engineering plastics
In the property indices such as dispersibility, interface bond strength, fire proofing mechanical strength.
Preparation flow is as follows：
（1）Boric acid is mixed with end hydroxyl silicone oil and small molecule siloxanes in proportion, heating is allowed to dissolve.Then by milling and
Negative pressure makes small-molecule substance be loaded into modified halloysite nanotubes cavity, obtains the galapectite nanometer of load small-molecule substance
Pipe.Cross-linking reaction under concentrated sulfuric acid catalyst generates the halloysite nanotubes for loading poly- boric acid silicone oil ester.
（2）It is reacted under certain condition with above-mentioned product with phosphorus oxychloride, obtains angstrom for loading poly- phosphorus Borosiloxane
Lip river stone nanotube.
Regulate and control the molecular characterization of poly- phosphorus Borosiloxane, phosphorus, boron, element silicon composition ratio, the degree of polymerization, cross-linked structure with
Itself and the compound rear good flame retardant property of engineering plastics are realized in composite load behavior of the crosslinking degree to itself and halloysite nanotubes
（Limit oxygen index presses down cigarette, at charcoal, peak value rate of heat release）And material mechanical performance, by the type for adjusting organosiloxane（Side
Base radical species）, three kinds of constituent contents of phosphorus borosilicate and the load capacity of composition ratio, poly- phosphorus Borosiloxane in halloysite nanotubes
And the parameters such as additive amount, it prepares and is suitable for the flame-retardant modified high-quality fire retardant series of the high molecular materials such as engineering plastics, rubber
Product, comprehensive flame retardant property reach V-0 grades of requirements of flame-retardant standard UL-94.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of nano-meter flame retardants, steps are as follows：
（1）The purification of halloysite nanotubes：Galapectite powder is added under stiring containing 1% polyacrylamide（Molecular weight is
1000 000）In aqueous solution, 2h is stirred, 10% suspension is made, 100 mesh screen suspension remove sediment；Gained suspends
Liquid centrifuge, rotating speed 6000r/min, sediment with the originally water washing of 10 times of volumes, centrifuge again again,
Rotating speed is 6000r/min, and dry 12h at 60 DEG C of obtained sediment crosses 400 mesh sieve, obtain pipe range concentrate on 200-800nm,
The halloysite nanotubes dusty material of internal diameter 5-20nm, outer diameter 10-80nm；Halloysite nanotubes are calcined into 6h at 200 DEG C,
Obtain pure halloysite nanotubes；
（2）The surface modification treatment of halloysite nanotubes obtains halloysite nanotubes powder；
（3）Boric acid powder after will be fine ground and hydroxy silicon oil（HO[(CH3)2SiO]nH）By certain mass than mixing 1:1 ~ 20 is mixed
It closes, is heated to 80 ~ 100 DEG C, stirring is allowed to dissolve, and obtains boric acid silicon oil solution；
（4）The halloysite nanotubes powder of surface-modified processing and boric acid silicon oil solution are pressed 5 ~ 10:1 mass ratio mixing,
30 ~ 60min is handled after milling under the negative pressure of 100 ~ 1000Pa；Or by the halloysite nanotubes powder of surface modification treatment with
Boric acid silicon oil solution presses 5 ~ 10:1 mass ratio mixing, adds diphenyl silanediol, in the negative pressure of 100-1000Pa after milling
30 ~ 120min is handled under lower or 10Pa vacuum；With back mill side instill the concentrated sulfuric acid（The concentrated sulfuric acid is 1 with boric acid mass ratio:20~
100）, obtain the halloysite nanotubes powder of load boric acid silicone oil ester；
（5）By the halloysite nanotubes powder and phosphorus oxychloride in mass ratio 10 ~ 50 of the obtained poly- boric acid silicone oil ester of load:1
Ratio mixes in anhydrous conditions, is vigorously stirred, and reacts 10 ~ 120min, is then heated to 90 ~ 105 DEG C, keeps 30min, dry
Obtain loading the halloysite nanotubes powder of poly- phosphorus Borosiloxane afterwards（Nano-meter flame retardants）.
Preferably, the step（2）The surface modification treatment of middle halloysite nanotubes is：Surface hydroxylation modification, surface
Organic-silylation, organic amine surface modification, quaternary alkylphosphonium salts surface are modified one such.
Preferably, the step（3）Middle hydroxy silicon oil（HO[(CH3)2SiO]nH）The value of middle n is：3~12.
Preferably, the method and step that the surface hydroxylation is modified is as follows：
Dry halloysite nanotubes are immersed in the sodium hydroxide solution of 0.2mol/L, is stirred at room temperature after ultrasonic disperse 30min
The mass volume ratio of 10h, halloysite nanotubes and sodium hydroxide solution is 1:2.5g/L；After reaction with 6000r/min's
Reaction solution is centrifuged 5min by rotating speed, discards upper layer lye, is washed with water between pH is 7 ~ 8, by obtained solid 60
It is DEG C dry for 24 hours, obtain the halloysite nanotubes powder of surface hydroxylation.
Preferably, the method and step of the surface organic-silylation is as follows：
Be separately added into halloysite nanotubes powder and chlorosilane through surface hydroxylation in acetone soln, halloysite nanotubes and
The mass ratio of chlorosilane is 1:1 ~ 2, the mass percent of galapectite is 0.1%, is stirred at reflux 3h；Product is true at 60 DEG C through filtering
Sky is dry for 24 hours, obtains the halloysite nanotubes powder of surface silanization.
Preferably, the method and step that the organic amine surface is modified is as follows：
Halloysite nanotubes of the purifying after dry are added to the ethanol solution of organic amine substance under stirring or ultrasonication
In, the mass volume ratio of halloysite nanotubes and alcohol is 1:The mass volume ratio of 100g/mL, organic amine and alcohol is 1.8:100g/
The mass ratio of mL, halloysite nanotubes and organic amine substance is 10:1；After being uniformly dispersed, removed in 70 DEG C of rotary evaporation dryings
Alcohol is removed, bulk sample is obtained, is dried in vacuo the galapectite nanometer for obtaining area load organic amine for 24 hours after levigate at 60 DEG C
Pipe powder.
Preferably, the method and step that the quaternary alkylphosphonium salt surface is modified is as follows：
Dry halloysite nanotubes are added in the alcoholic solution of small molecule quaternary alkylphosphonium salt under stirring or ultrasonication, galapectite
The mass volume ratio of nanotube and alcohol is 1:The mass volume ratio of 100g/mL , quaternary alkylphosphonium salts and alcohol is 3:100g/mL, galapectite are received
Mitron is He the mass ratio of quaternary alkylphosphonium salt is 5:1；After being uniformly dispersed, alcohol is dried and removed in 70 DEG C of rotary evaporations, obtains bulk sample,
60 DEG C of vacuum drying for 24 hours, obtain the halloysite nanotubes powder of area load quaternary alkylphosphonium salt after levigate.
Preferably, the organic amine substance is：Diethanol amine, triethanolamine, diethylenetriamine, triethylene tetramine, four
One or more of five amine of ethylene, polyethyleneimine, polyacrylamide mix.
Advantageous effect：
（1）The present invention uses carrier of the galapectite as fire retardant, it is easy to accomplish nano-powder, it is safe and non-toxic, and belong to environment
Harmless inorganic substances.
（2）The galapectite material that the present invention uses, relative to other artificial synthesized nanotube modified material such as carbon nanotubes,
Graphene etc. is a kind of nature largely existing inorganic mineral, have low production cost, preparation method it is simple, without environment
The advantages such as pollution.
（3）The galapectite that the present invention uses is reacted by surface hydroxylation carries out hydroxylating by halloysite nanotubes surface,
Then halloysite nanotubes surface is chemically modified using a variety of surface modifying methods, such as organic-silylation processing, organic
Modified, quaternary alkylphosphonium salt modification of amine etc., to improve halloysite nanotubes absorption and affine performance.
（4）The preparation method of poly- phosphorus Borosiloxane fire retardant used in the present invention not only can get a kind of novel organic
Fire retardant, and reaction process flow is simple, is swift in response, and reaction efficiency is high, product yield high.Meanwhile by adjusting synthesis
Preparation process optimizes three kinds of its phosphorus, boron, silicon element compositions, can have notable flame retardant effect.
Specific implementation mode
The purification of halloysite nanotubes：Galapectite powder is added under stiring containing 1% polyacrylamide（Molecular weight is
1000 000）In aqueous solution, 2h is stirred, 10% suspension is made, 100 mesh screen suspension remove sediment；Gained suspends
Liquid centrifuge, rotating speed 6000r/min, sediment with the originally water washing of 10 times of volumes, centrifuge again again,
Rotating speed is 6000r/min, and dry 12h at obtained sediment is 60 DEG C in temperature crosses 400 mesh sieve, obtains pipe range and concentrate on
The pure halloysite nanotubes dusty material of 200-800nm, internal diameter 5-20nm, outer diameter 10-80nm；Halloysite nanotubes are existed
6h is calcined at 200 DEG C, obtains pure halloysite nanotubes.
Embodiment 1
1）The surface hydroxylation of halloysite nanotubes is modified
Room temperature after ultrasonic disperse 30min in the sodium hydroxide solution of dry pure halloysite nanotubes immersion 0.2mol/L is stirred
Mix 10h, the mass volume ratio of halloysite nanotubes and sodium hydroxide solution is 1: 2.5g/L.After reaction with 6000r/min
Rate reaction solution is centrifuged into 5min, discard upper layer lye, be washed with water until supernatant pH between 7-8.By gained
At 60 DEG C, drying for 24 hours, obtains the halloysite nanotubes powder of surface hydroxylation to solid.
2）Boric acid powder after will be fine ground and hydroxy silicon oil（n=3）In mass ratio 1:3 mixing, are heated to 80 DEG C, stirring makes
Dissolving, obtain boric acid silicon oil solution.
3）By the halloysite nanotubes powder handled through surface hydroxylation and boric acid silicon oil solution by 10:1 mass ratio is mixed
It closes, 30min is handled under the negative pressure of 1000Pa after milling.With back mill side instill the concentrated sulfuric acid（The concentrated sulfuric acid and boric acid of addition
Mass ratio is 1:100）Obtain loading the halloysite nanotubes powder of poly- boric acid silicone oil ester afterwards.
4）By the halloysite nanotubes powder and phosphorus oxychloride in mass ratio 50 of the obtained poly- boric acid silicone oil ester of load:1
Ratio mixes in anhydrous conditions, is vigorously stirred, and reacts 10min.105 DEG C are subsequently heated to, obtains loading poly- phosphorus boron after dry
The halloysite nanotubes powder of siloxanes（Nano-meter flame retardants）.
Embodiment 2
1）The surface organic-silylation of halloysite nanotubes
Be separately added into halloysite nanotubes powder and chlorosilane through surface hydroxylation in acetone soln, halloysite nanotubes and
The mass ratio of chlorosilane is 1:1.2, the mass percent of galapectite is 0.1%, is stirred at reflux 3h.Product is true at 60 DEG C through filtering
Sky is dry for 24 hours, obtains the halloysite nanotubes powder of surface silanization.
2）Boric acid powder after will be fine ground and hydroxy silicon oil（n=12）In mass ratio 1:20 mixing are heated to 100 DEG C, stirring
It is allowed to dissolve, obtains boric acid silicon oil solution.
3）The halloysite nanotubes powder handled through surface organic-silylation and boric acid silicon oil solution are pressed 5:1 mass ratio
Mixing, 1h is handled after milling under the negative pressure of 100Pa.With back mill side instill the concentrated sulfuric acid（The concentrated sulfuric acid of addition and boric acid matter
Amount is than being 1:50）Obtain loading the halloysite nanotubes powder of poly- boric acid silicone oil ester afterwards.
4）By the halloysite nanotubes powder and phosphorus oxychloride in mass ratio 10 of the obtained poly- boric acid silicone oil ester of load:1
Ratio mixes in anhydrous conditions, is vigorously stirred, and reacts 30min.100 DEG C are subsequently heated to, obtains loading poly- phosphorus boron after dry
The halloysite nanotubes powder of siloxanes（Nano-meter flame retardants）.
Embodiment 3
1）The organic amine surface of halloysite nanotubes is modified
Halloysite nanotubes of the purifying after dry are added to organic amine substance under stirring or ultrasonication（Diethanol amine,
One or both of triethanolamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethyleneimine, polyacrylamide
Above mixing）Ethanol solution in, the mass volume ratio of halloysite nanotubes and alcohol is 1:100g/mL, organic amine and alcohol
Mass volume ratio is 1.8:The mass ratio of 100g/mL, halloysite nanotubes and organic amine substance is 10:1.It waits being uniformly dispersed
Afterwards, alcohol is dried and removed in 70 DEG C of rotary evaporations, obtains bulk sample, is dried in vacuo at 60 DEG C for 24 hours after levigate, it is negative to obtain surface
The halloysite nanotubes powder of organic amine is carried.
2）Boric acid powder after will be fine ground and hydroxy silicon oil（n=9）In mass ratio 1:20 mixing are heated to 100 DEG C, stirring
It is allowed to dissolve, obtains boric acid silicon oil solution.
3）The halloysite nanotubes powder of area load organic amine and boric acid silicon oil solution are pressed 5:1 mass ratio is mixed
It closes, adds diphenyl silanediol, 2h is handled under the negative pressure of 1000Pa after milling.With back mill side instill the concentrated sulfuric acid（Add
The concentrated sulfuric acid entered is 1 with boric acid mass ratio:20）Obtain loading the halloysite nanotubes powder of poly- boric acid silicone oil ester afterwards.
4）By the halloysite nanotubes powder and phosphorus oxychloride in mass ratio 30 of the obtained poly- boric acid silicone oil ester of load:1
Ratio mixes in anhydrous conditions, is vigorously stirred, and reacts 30min.100 DEG C are subsequently heated to, obtains loading poly- phosphorus boron after dry
The halloysite nanotubes powder of siloxanes（Nano-meter flame retardants）.
Embodiment 4
1）Halloysite nanotubes quaternary alkylphosphonium salts surface is modified
Dry halloysite nanotubes are added in the alcoholic solution of small molecule quaternary alkylphosphonium salt under stirring or ultrasonication, galapectite
The mass volume ratio of nanotube and alcohol is 1:The mass volume ratio of 100g/mL , quaternary alkylphosphonium salts and alcohol is 3:100g/mL, galapectite are received
Mitron is He the mass ratio of quaternary alkylphosphonium salt is 5:1.After being uniformly dispersed, alcohol is dried and removed in 70 DEG C of rotary evaporations, obtains bulk sample,
60 DEG C of vacuum drying for 24 hours, obtain the halloysite nanotubes powder of area load quaternary alkylphosphonium salt after levigate.
2）Boron trioxide powder after will be fine ground presses 1 with advance:The hydroxy silicon oil of 1 ratio mixing（n=6）, three ethoxy of methyl
Base silane solution in mass ratio 1:5 mixing are heated to 90 DEG C, and stirring is allowed to dissolve, and obtains boric acid silicon oil solution.
3）The halloysite nanotubes powder of area load quaternary alkylphosphonium salt and boric acid silicon oil solution are pressed 5:1 mass ratio mixing,
Diphenyl silanediol is added, 0.5h is handled under the vacuum condition of 10Pa after milling.With back mill side instill the concentrated sulfuric acid（Add
The concentrated sulfuric acid entered is 1 with boric acid mass ratio:80）Obtain loading the halloysite nanotubes powder of poly- boric acid silicone oil ester afterwards.
4）By the halloysite nanotubes powder and phosphorus oxychloride in mass ratio 10 of the obtained poly- boric acid silicone oil ester of load:1
Ratio mixes in anhydrous conditions, is vigorously stirred, and reacts 2h.90 DEG C are subsequently heated to, obtains loading poly- phosphorus borosilicate oxygen after dry
The halloysite nanotubes powder of alkane（Nano-meter flame retardants）.
Claims (8)
1. a kind of preparation method of nano-meter flame retardants, includes the following steps：
（1）The purification of halloysite nanotubes：Galapectite powder is added under stiring containing 1% polyacrylamide（Molecular weight is
1000 000）In aqueous solution, 2h is stirred, 10% suspension is made, 100 mesh screen suspension remove sediment；Gained suspends
Liquid centrifuge, rotating speed 6000r/min, sediment with the originally water washing of 10 times of volumes, centrifuge again again,
Rotating speed is 6000r/min, and dry 12h at 60 DEG C of obtained sediment crosses 400 mesh sieve, obtain pipe range concentrate on 200-800nm,
The halloysite nanotubes powder of internal diameter 5-20nm, outer diameter 10-80nm；It is calcined into 6h at 200 DEG C, pure galapectite is obtained and receives
Mitron；
（2）Halloysite nanotubes surface modification treatment obtains modified halloysite nanotubes powder；
（3）Boric acid powder after will be fine ground and hydroxy silicon oil（HO[(CH3)2SiO]nH）In mass ratio 1:1 ~ 20 mixing, is heated to
80 ~ 100 DEG C, stirring is allowed to dissolve, and obtains boric acid silicon oil solution；
（4）The halloysite nanotubes powder of surface-modified processing and boric acid silicon oil solution are pressed 5 ~ 10:1 mass ratio mixing,
30 ~ 60min is handled after milling under the negative pressure of 100 ~ 1000Pa；Or by the halloysite nanotubes powder of surface modification treatment with
Boric acid silicon oil solution presses 5 ~ 10:1 mass ratio mixing, adds diphenyl silanediol, in the negative pressure of 100 ~ 1000Pa after milling
30 ~ 120min is handled under lower or 10Pa vacuum；With back mill side instill the concentrated sulfuric acid（The concentrated sulfuric acid is 1 with boric acid mass ratio:20~
100）, obtain the halloysite nanotubes powder for loading poly- boric acid silicone oil ester；
（5）By the halloysite nanotubes powder and phosphorus oxychloride in mass ratio 10 ~ 50 of the obtained poly- boric acid silicone oil ester of load:1
Ratio mixes in anhydrous conditions, is vigorously stirred, and reacts 10 ~ 120min, is then heated to 90 ~ 105 DEG C, keeps 30min, dry
Obtain loading the halloysite nanotubes powder of poly- phosphorus Borosiloxane afterwards（Nano-meter flame retardants）.
2. a kind of preparation method of nano-meter flame retardants according to claim 1, which is characterized in that the step（2）In angstrom Lip river
The surface modification treatment of stone nanotube is：Surface hydroxylation modification, surface organic-silylation, organic amine surface modification, quaternary alkylphosphonium salts
Surface is modified one such.
3. a kind of preparation method of nano-meter flame retardants according to claim 1, which is characterized in that the step（3）Middle hydroxyl
Silicone oil（HO[(CH3)2SiO]nH）The value of middle n is：3~12.
4. step according to claim 2（2）The surface modification treatment of middle halloysite nanotubes, which is characterized in that the table
The method and step that face hydroxylating is modified is as follows：
Dry halloysite nanotubes are immersed in the sodium hydroxide solution of 0.2mol/L, is stirred at room temperature after ultrasonic disperse 30min
The mass volume ratio of 10h, halloysite nanotubes and sodium hydroxide solution is 1:2.5g/L；After reaction with 6000r/min's
Reaction solution is centrifuged 5min by rotating speed, discards upper layer lye, is washed with water between pH is 7 ~ 8, by obtained solid 60
It is DEG C dry for 24 hours, obtain the halloysite nanotubes powder of surface hydroxylation.
5. step according to claim 2（2）The surface modification treatment of middle halloysite nanotubes, which is characterized in that the table
The method and step of face organic-silylation is as follows：
The halloysite nanotubes powder through surface hydroxylation is separately added into acetone soln, the mass percent of galapectite is
0.1%, it is added chlorosilane after being dispersed with stirring, the mass ratio of halloysite nanotubes and chlorosilane is 1:1 ~ 2, it is stirred at reflux 3h；Product
Through filtering, at 60 DEG C, vacuum drying for 24 hours, obtains the halloysite nanotubes powder of surface silanization.
6. step according to claim 2（2）The surface modification treatment of middle halloysite nanotubes, which is characterized in that described to have
The method and step that machine amine surface is modified is as follows：
Halloysite nanotubes of the purifying after dry are added to the ethanol solution of organic amine substance under stirring or ultrasonication
In, the mass volume ratio of halloysite nanotubes and alcohol is 1:The mass volume ratio of 100g/mL, organic amine and alcohol is 1.8:100g/
The mass ratio of mL, halloysite nanotubes and organic amine substance is 10:1；After being uniformly dispersed, removed in 70 DEG C of rotary evaporation dryings
Alcohol is removed, bulk sample is obtained, is dried in vacuo the galapectite nanometer for obtaining area load organic amine for 24 hours after levigate at 60 DEG C
Pipe powder.
7. step according to claim 2（2）The surface modification treatment of middle halloysite nanotubes, which is characterized in that the season
The method and step that phosphonium salt surface is modified is as follows：
Dry halloysite nanotubes are added in the alcoholic solution of small molecule quaternary alkylphosphonium salt under stirring or ultrasonication, galapectite
The mass volume ratio of nanotube and alcohol is 1:The mass volume ratio of 100g/mL , quaternary alkylphosphonium salts and alcohol is 3:100g/mL, galapectite are received
Mitron is He the mass ratio of quaternary alkylphosphonium salt is 5:1；After being uniformly dispersed, alcohol is dried and removed in 70 DEG C of rotary evaporations, obtains bulk sample,
60 DEG C of vacuum drying for 24 hours, obtain the halloysite nanotubes powder of area load quaternary alkylphosphonium salt after levigate.
8. the method that organic amine surface is modified according to claim 6, which is characterized in that the organic amine substance is：Two
One in ethanol amine, triethanolamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, polyethyleneimine, polyacrylamide
Kind or two or more mixing.
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