CN106398020A - Preparation method of nano composite flame retardant for soft PVC - Google Patents

Preparation method of nano composite flame retardant for soft PVC Download PDF

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CN106398020A
CN106398020A CN201610723392.3A CN201610723392A CN106398020A CN 106398020 A CN106398020 A CN 106398020A CN 201610723392 A CN201610723392 A CN 201610723392A CN 106398020 A CN106398020 A CN 106398020A
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ldhs
znmgal
flame retardant
preparation
soft pvc
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杨保俊
尚松川
王百年
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Hefei University of Technology
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Hefei University of Technology
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)

Abstract

The invention discloses a preparation method of a nano composite flame retardant for soft PVC, first, a fast nucleation / crystallization method is used for preparing ZnMgAl-LDHs, then sodium oleate as a modifier is used for surface modification of the ZnMgAl-LDHs, and Sb2O3 powder and the modified ZnMgAl-LDHs sample are mixed in a ball milling tank for ball milling to obtain the Sb2O3-ZnMgAl-LDHs nano composite flame retardant. The composite material prepared by the method has good flame retardant property and mechanical property, and the flame retardant effect is obviously better than that of general flame retardant materials.

Description

A kind of preparation method of the composite nanometer flame retardant for soft pvc
First, technical field
The present invention relates to a kind of preparation method of fire retardant, specifically a kind of nano composite fire retardant for soft pvc The preparation method of agent, and the fire-retardant and mechanical performance in flexible PVC material is evaluated to it.
2nd, background technology
Polrvinyl chloride (Polyvinyl chloride, PVC) is as important commercial thermoplastic's high polymer, its mechanical property Excellent, electrical insulating property is good, stable chemical nature, and price is excellent honest and clean, is widely used in the fields such as building materials, tubing, electric wire.Firmly Matter PVC this as self-extinguishment row material, but soft pvc is due to adding the plasticizer such as substantial amounts of DOP, and its limited oxygen index (LOI) is significantly Reduce and become combustible material, meet fiery easy firing, produce a large amount of smog and toxic gas, so that soft pvc is existed in the application perhaps Many potential hazards.As for the fire retardant of soft pvc it is desirable to it has highly effective flame-retardant and the suppression performance such as cigarette concurrently, and to soft pvc itself Mechanical impact less.
Houghite (LDHs), also known as layered double-hydroxide, is an anionoid intercal type material.The layer of houghite Plate is by MO6Octahedron shares seamed edge and is formed, positively charged, and interlayer is anion and a small amount of crystalline water molecules, the master being formed Object structure assumes neutrality.LDHs has excellent anion exchange performance and heat stability, catalysis, ion exchange, Absorption, many fields such as fire-retardant are applied.
LDHs be used as fire retardant when, have Halogen, nontoxic, do not produce corrosive gas and have significant smoke suppressing etc. excellent Point, is a class environment friendly flame retardant.But, it is big, fire-retardant that LDHs uses fashion to there is addition as inorganic additive flame retardant The low outstanding problem of efficiency；Meanwhile, LDHs surface hydrophilic oleophobic, and polymeric matrix poor compatibility, to flame-proof composite material machine Tool performance impact is larger.Therefore, for improving the flame retarding efficiency of LDHs, improve composite machinery performance, typically need before use Carry out surface modification.
Sb2O3It is one kind efficiently inorganic additive flame retardant, its fire-retardant application and development in the high polymers such as soft pvc is relatively Early, also more ripe.Sb2O3Can be independently operated, when using as fire retardant and also can compound cooperative flame retardant with other fire retardants, extensively General fire-retardant etc. for brightening agent, fabric, soft pvc.But Sb simultaneously2O3There is also increasing cigarette, poisonous, expensive and resource-constrained, Easily assemble in polymeric matrix, the deficiency such as dispersibility, poor compatibility.Therefore, develop cheap, good flame retardation effect fire retardant to substitute Or part substitutes Sb2O3Become the study hotspot of soft pvc flame retardant area.
3rd, content of the invention
The invention provides a kind of preparation method of the composite nanometer flame retardant for soft pvc, technology to be solved is asked Topic improves its fire resistance on the premise of being to ensure that soft pvc mechanical performance.
The present invention is used for the preparation method of the composite nanometer flame retardant of soft pvc, initially with fast nucleation/crystallization method preparation ZnMgAl-LDHs, then carries out surface modification for modifying agent to ZnMgAl-LDHs with enuatrol, then by Sb2O3Powder and modification The mixing and ball milling in ball grinder of ZnMgAl-LDHs sample afterwards, obtains Sb2O3- ZnMgAl-LDHs composite nanometer flame retardant.Specifically Comprise the steps：
1st, 0.06mol zinc nitrate and 0.06mol magnesium nitrate are added in 200mL deionized water, prepare and obtain saline solution A； 0.06mol sodium aluminate and 0.03mol sodium carbonate are added in 300mL deionized water, prepares and obtain aqueous slkali B；Constant temperature water bath 65 Under the conditions of DEG C, described saline solution A is mixed with described aqueous slkali B, stir 3～5min, adjusted with 0.1～0.3mol/L NaOH solution Section pH value of reaction system, to 9～11, continues stirring dynamic crystallization 1h, static ageing 24h, filtration, washing, and gained filter cake is in 70 DEG C Lower drying, is obtained white ZnMgAl-LDHs sample；
2nd, the undried ZnMgAl-LDHs filter cake that step 1 is obtained is distributed to the Oleic acid of 600mL 0.2～1.2g/L In sodium solution, with the H of 0.1～0.3mol/L at 65 DEG C of constant temperature water bath2SO4Solution adjusts pH value of reaction system to 5～7, stirs 1h, filters, washs, gained filter cake is dried at 70 DEG C, modification ZnMgAl-LDHs is obtained, is white powder；
3rd, by Sb2O3Powder is mixed in ball grinder with step 2 gained modification ZnMgAl-LDHs, adds dehydrated alcohol, Rotational speed of ball-mill 350～650r/min, ratio of grinding media to material 1:1～3:Ball milling 6～14h under conditions of 1, obtains Sb at 70 DEG C after being dried2O3- ZnMgAl-LDHs composite nanometer flame retardant.
Sb2O3The addition of powder is Sb2O3The 5～15% of-ZnMgAl-LDHs composite nanometer flame retardant quality.
The composite nanometer flame retardant that the present invention is obtained is applied in soft pvc, prepares soft pvc nano fire-retarding composite material, Detection data shows that prepared composite has good fire resistance and mechanical performance.
Compared with the prior art, beneficial effects of the present invention are embodied in：
For the fire retardant of soft pvc, it is needed to have the performances such as suppression cigarette, highly effective flame-retardant, and the machine to soft pvc itself Tool performance impact is less.When LDHs is used as fire retardant and uses, Halogen, nontoxic, do not produce corrosive gas and have significantly Smoke suppressing, is a class environment friendly flame retardant, typically need to carry out surface modification before use, improves the flame retarding efficiency of LDHs, changes Kind composite machinery performance；Sb2O3It is one kind efficiently inorganic additive flame retardant, but Sb simultaneously2O3There is also and such as increase Cigarette, poisonous, expensive and resource-constrained, easily assemble in polymeric matrix, and the deficiency such as dispersibility, poor compatibility therefore, is opened Send out cheap, environmental protection, the fire retardant replacement of good flame retardation effect or partly substitute Sb2O3Become the study hotspot of soft pvc flame retardant area. It is less that the fire retardant of present invention preparation has a fire retardant addition, and flame retarding efficiency is high, and to power such as elongation at break, tensile strengths Learn the less feature of performance impact.
4th, brief description
Fig. 1 is rear before modified the ZnMgAl-LDHs, (Sb of embodiment 2 preparation of the embodiment of the present invention 1 preparation2O3)10- The XRD spectra of ZnMgAl-LDHs composite nanometer flame retardant.As can be seen from Figure 1 before modified after ZnMgAl-LDHs in relatively low 2 θ All there is the low indices of crystallographic plane (00l) diffraction maximum of feature at place, respectively typical brucite characteristic diffraction peak (003), (006), (009), show that prepared ZnMgAl-LDHs sample has more regular flaggy pattern.By bragg's formula (dhkl=n λ/ 2sin θ, wherein dhklFor interplanar distance, n=1 is diffraction progression, and λ=0.15405nm is the wavelength of target used, and θ is the angle of diffraction) After calculating before modified, LDHs interlayer distance is respectively：d(003)=0.8625,0.8690nm.By d(003)Deduct laminate thickness (about 0.48nm), obtain interlamellar spacing and be respectively 0.38 and 0.39nm, illustrate that enuatrol is by the Surface coating to ZnMgAl-LDHs And reach modified effect, it is not inserted into ZnMgAl-LDHs interlayer.(Sb through ball milling preparation2O3)10- ZnMgAl-LDHs is nano combined The diffraction maximum of the ZnMgAl-LDHs in fire retardant is significantly broadened, illustrates that the ZnMgAl-LDHs structure after high speed ball milling occurs no Amorphization and nanorize.Meanwhile, (Sb2O3)10In the XRD figure of-ZnMgAl-LDHs composite nanometer flame retardant 2 θ be 13.8 °, At 27.8 °, 32.1 °, 35.1 °, 46.0 ° and 54.7 °, Sb occurs2O3(111), (222), (400), (311), (440) and (622) characteristic diffraction peak of crystal face.
Rear before modified the ZnMgAl-LDHs, (Sb of embodiment 2 preparation that Fig. 2 obtains for embodiment 12O3)10-ZnMgAl- LDHs composite nanometer flame retardant and Sb2O3FT-IR figure.Modified ZnMgAl- be can be seen that by the FT-IR figure of ZnMgAl-LDHs The FT-IR in figure of LDHs occurs in that 2919cm-1、2840cm-1、1521cm-1Three new absworption peaks, respectively saturated alkane- CH3、-CH2C-H is symmetrical and asymmetrical stretching vibration characteristic absorption peak, and-COO- asymmetric stretching vibration peak, show Oleic acid It is present in ZnMgAl-LDHs stable sodium.Wave number 708cm-1For Sb2O3Characteristic absorption peak, (Sb2O3)10- ZnMgAl-LDHs sample In 703cm on the FT-IR figure of product-1Place occurs in that the characteristic absorption peak of Sb-O key, illustrates Sb2O3Presence.
Fig. 3 is rear before modified ZnMgAl-LDHs (a＆b), (Sb of embodiment 2 preparation of embodiment 1 preparation2O3)10- ZnMgAl-LDHs (d), (Sb of embodiment 3 preparation2O3)5- ZnMgAl-LDHs (c) and (Sb of embodiment 4 preparation2O3)15- The FESEM figure of ZnMgAl-LDHs (e).Can be seen that from Fig. 3 (a), (b)：ZnMgAl-LDHs sample presents significantly before modified Irregularly flake, rough surface；Modified ZnMgAl-LDHs smooth surface, lamella regularity improves, and particle diameter diminishes.From Fig. 3 C (), (d), (e) can be seen that：Through the Sb after high speed ball milling2O3- ZnMgAl-LDHs sample be mainly shown as graininess, lamellar Pattern fades away, and grain diameter reduces, wherein with (Sb2O3)10The particle diameter of-ZnMgAl-LDHs sample is minimum.
Fig. 4 is not added with soft pvc composite (a) of fire retardant and the modification adding 6 parts of embodiment 1 preparations for embodiment 1 ZnMgAl-LDHs (b＆c), (Sb of embodiment 2 preparation in front and back2O3)10The soft pvc nano fire-retarding composite material of-ZnMgAl-LDHs The TG curve of (d).From fig. 4, it can be seen that the total weight-loss ratio of soft pvc composite being not added with fire retardant is 75.82%, add ZnMgAl-LDHs, modified ZnMgAl-LDHs and (Sb2O3)10The soft pvc anti-flaming nano composite material of-ZnMgAl-LDHs always loses Again rate be respectively 69.00%, 68.33%, 65.44%, illustrate add ZnMgAl-LDHs, modification ZnMgAl-LDHs and (Sb2O3)10The heat stability of the soft pvc anti-flaming nano composite material of-ZnMgAl-LDHs increases.
5th, specific embodiment
The present invention adopts D/Max2500 type X-ray diffractometer (Rigaku company, CuK α, λ=0.15405nm) to characterize The crystallization property (XRD, 5 °/min of sweep speed, sweep limitss (2 θ) are 5～70 °) of sample；With Nicolet6700 type Fourier Infrared spectrum property (FT-IR, KBr tabletting, the wave number model of transform infrared spectroscopy instrument (U.S. Buddhist nun high-tensile strength instrument company) determination sample Enclose 400～4000cm-1)；Observed with SU8020 type scanning electron microscope (FESEM, accelerating potential 5kV, HIT) The microscopic appearance of sample and elementary composition；Measured with STA449F3 type thermogravimetric analyzer (German Nai Chi instrument manufacturing company limited) Heat stability (TG, the N of sample2Atmosphere, 10 DEG C/min of heating rate, 35～700 DEG C of test temperature).
Detected before modified with HC-2 type oxygen index instrument (analytical tool factory of Jiangning county) by GB/T 2406.2-2009 ZnMgAl-LDHs/ soft pvc and Sb afterwards2O3The limited oxygen index of-LDHs/ soft pvc nano flame retardant nano composite material batten；Press UL-94 vertical burn test standard detects batten with CZF-3 type vertical combustion analyzer (analytical tool factory of Jiangning county) Vertical combustion performance；By GB/T 1040-92, with CMT4304 type electronic universal tester, (Shenzhen newly thinks carefully that material tests have Limit company) the detection tensile strength of batten and elongation at break.
Embodiment 1：
1st, 0.06mol zinc nitrate and 0.06mol magnesium nitrate are added in 200mL deionized water, prepare and obtain saline solution A； 0.06mol sodium aluminate and 0.03mol sodium carbonate are added in 300mL deionized water, prepares and obtain aqueous slkali B；Constant temperature water bath 65 Under the conditions of DEG C, described saline solution A is mixed with described aqueous slkali B, stir 3～5min, adjusted with 0.2mol/L NaOH solution anti- Answer system pH to 10, continue stirring dynamic crystallization 1h, static ageing 24h, filter, wash, gained filter cake is dried at 70 DEG C, White ZnMgAl-LDHs sample is obtained；
2nd, by step 1 be obtained undried ZnMgAl-LDHs filter cake be distributed to 600mL 0.6g/L enuatrol molten In liquid, with the H of 0.2mol/L at 65 DEG C of constant temperature water bath2SO4Solution adjusts pH value of reaction system to 6, stirs 1h, filters, washs, Gained filter cake is dried at 70 DEG C, modification ZnMgAl-LDHs is obtained, is white powder；
3rd, step 2 gained modification ZnMgAl-LDHs is placed in ball grinder, adds dehydrated alcohol, in rotational speed of ball-mill 500r/ Min, ratio of grinding media to material 2:Ball milling 10h under conditions of 1, obtains modified ZnMgAl-LDHs nano-meter flame retardantses at 70 DEG C after being dried.
4th, as a comparison, step 1 gained ZnMgAl-LDHs is placed in ball grinder, adds dehydrated alcohol, in rotational speed of ball-mill 500r/min, ratio of grinding media to material 2:Ball milling 10h under conditions of 1, obtains unmodified ZnMgAl-LDHs nano flame retardant after being dried at 70 DEG C Agent.
Add 0 mass parts fire retardant, the resistance of 6 mass parts unmodified ZnMgAl-LDHs nanometer respectively in 100 mass parts PVC Combustion agent, 6 mass parts modification ZnMgAl-LDHs nano-meter flame retardantses, obtain soft pvc composite, unmodified ZnMgAl- respectively LDHs/ soft pvc nano fire-retarding composite material, modified ZnMgAl-LDHs/ soft pvc nano fire-retarding composite material, and carry out LOI value, The performance detections such as UL-94 vertical combustion, elongation at break, tensile strength (are shown in Table 1).Be can be seen that by table 1 data：It is not added with hindering The soft pvc composite of combustion agent and the soft pvc nano flame retardant composite wood adding rear ZnMgAl-LDHs nano-meter flame retardantses powder before modified The vertical combustion grade (UL-94) of material all reaches V-0 level, and has self-extinguishment；After before modified, the interpolation of ZnMgAl-LDHs all carries The high LOI value of composite, adds ZnMgAl-LDHs/ soft pvc nano flame retardant prepared by 6 parts of unmodified ZnMgAl-LDHs and answers The LOI value of condensation material is improved to 28.5% by 27%, and elongation at break is reduced to 130% by 162%, tensile strength by 13.7MPa reduces to 11.5MPa；Add modified ZnMgAl-LDHs/ soft pvc nanometer resistance prepared by 6 parts of modified ZnMgAl-LDHs The LOI value of retardant composite material is improved to 29% by 27%, and elongation at break is reduced to 195% by 162%, tensile strength by 13.7MPa reduces to 17.5MPa, compared with unmodified ZnMgAl-LDHs, the flame retarding efficiency of modified ZnMgAl-LDHs fire retardant Height, the mechanical properties data such as elongation at break, tensile strength is obviously improved.
Table 1
Note：Index number represents Sb2O3Account for the mass percent of composite nanometer flame retardant, such as " (Sb2O3)5-ZnMgAl- Following table numeral 5 expression Sb in LDHs/PVC nano fire-retarding composite material "2O3The mass percent accounting for composite nanometer flame retardant is 5%.
Embodiment 2：
1st, 0.06mol zinc nitrate and 0.06mol magnesium nitrate are added in 200mL deionized water, prepare and obtain saline solution A； 0.06mol sodium aluminate and 0.03mol sodium carbonate are added in 300mL deionized water, prepares and obtain aqueous slkali B；Constant temperature water bath 65 Under the conditions of DEG C, described saline solution A is mixed with described aqueous slkali B, stir 3～5min, adjusted with 0.2mol/L NaOH solution anti- Answer system pH to 10, continue stirring dynamic crystallization 1h, static ageing 24h, filter, wash, gained filter cake is dried at 70 DEG C, White ZnMgAl-LDHs sample is obtained；
2nd, by step 1 be obtained undried ZnMgAl-LDHs filter cake be distributed to 600mL 0.6g/L enuatrol molten In liquid, with the H of 0.2mol/L at 65 DEG C of constant temperature water bath2SO4Solution adjusts pH value of reaction system to 6, stirs 1h, filters, washs, Gained filter cake is dried at 70 DEG C, modification ZnMgAl-LDHs is obtained, is white powder；
3rd, by Sb2O3Powder is mixed in ball grinder with step 2 gained modification ZnMgAl-LDHs, adds dehydrated alcohol, Rotational speed of ball-mill 500r/min, ratio of grinding media to material 2:Ball milling 10h under conditions of 1, obtains (Sb at 70 DEG C after being dried2O3)10-ZnMgAl- LDHs composite nanometer flame retardant.Sb2O3The addition of powder is the 10% of composite nanometer flame retardant quality.
Add 6 mass parts (Sb in 100 mass parts PVC2O3)10- ZnMgAl-LDHs composite nanometer flame retardant, preparation obtains Obtain (Sb2O3)10- ZnMgAl-LDHs/ soft pvc nano fire-retarding composite material, and carry out LOI value, UL-94 vertical combustion, rupture and stretch The performance detections such as long rate, tensile strength (are shown in Table 1).Be can be seen that by table 1 data：(Sb2O3)10- ZnMgAl-LDHs/ soft pvc is received The vertical combustion grade (UL-94) of rice flame-proof composite material reaches V-0 level, and has self-extinguishment；(Sb2O3)10-ZnMgAl- The LOI value of LDHs/ soft pvc nano fire-retarding composite material is improved to 33.2% by 27%, elongation at break by 162% improve to 181%, tensile strength is improved to 15.9MPa by 13.7MPa, (Sb2O3)10The addition of-ZnMgAl-LDHs fire retardant is less, Flame retarding efficiency is high, and the mechanical properties data such as elongation at break, tensile strength is slightly lifted.
Embodiment 3：
1st, 0.06mol zinc nitrate and 0.06mol magnesium nitrate are added in 200mL deionized water, prepare and obtain saline solution A； 0.06mol sodium aluminate and 0.03mol sodium carbonate are added in 300mL deionized water, prepares and obtain aqueous slkali B；Constant temperature water bath 65 Under the conditions of DEG C, described saline solution A is mixed with described aqueous slkali B, stir 3～5min, adjusted with 0.2mol/L NaOH solution anti- Answer system pH to 10, continue stirring dynamic crystallization 1h, static ageing 24h, filter, wash, gained filter cake is dried at 70 DEG C, White ZnMgAl-LDHs sample is obtained；
2nd, by step 1 be obtained undried ZnMgAl-LDHs filter cake be distributed to 600mL 0.6g/L enuatrol molten In liquid, with the H of 0.2mol/L at 65 DEG C of constant temperature water bath2SO4Solution adjusts pH value of reaction system to 6, stirs 1h, filters, washs, Gained filter cake is dried at 70 DEG C, modification ZnMgAl-LDHs is obtained, is white powder；
3rd, by Sb2O3Powder is mixed in ball grinder with step 2 gained modification ZnMgAl-LDHs, adds dehydrated alcohol, Rotational speed of ball-mill 600r/min, ratio of grinding media to material 1:Ball milling 12h under conditions of 1, obtains (Sb at 70 DEG C after being dried2O3)5-ZnMgAl-LDHs Composite nanometer flame retardant.Sb2O3The addition of powder is the 5% of modified ZnMgAl-LDHs mass.
Add 7 mass parts (Sb in 100 mass parts PVC2O3)5- ZnMgAl-LDHs composite nanometer flame retardant, prepares (Sb2O3)5- ZnMgAl-LDHs/ soft pvc nano fire-retarding composite material, and carry out LOI value, UL-94 vertical combustion, extension at break The performance detections such as rate, tensile strength (are shown in Table 1).Result shows (Sb2O3)5- ZnMgAl-LDHs/ soft pvc nano flame retardant composite wood The vertical combustion grade (UL-94) of material reaches V-0 level, and has self-extinguishment；(Sb2O3)5- ZnMgAl-LDHs/ soft pvc nanometer hinders The LOI value of retardant composite material is improved to 31.8% by 27%, and elongation at break is improved to 184% by 162%, tensile strength by 13.7MPa improves to 16.0MPa, shows prepared (Sb2O3)5The addition of-ZnMgAl-LDHs composite nanometer flame retardant is relatively Few, the mechanical performance such as elongation at break, tensile strength has been lifted, and the LOI value of prepared nano fire-retarding composite material is substantially high Interpolation in rear ZnMgAl-LDHs before modified.
Embodiment 4：
1st, 0.06mol zinc nitrate and 0.06mol magnesium nitrate are added in 200mL deionized water, prepare and obtain saline solution A； 0.06mol sodium aluminate and 0.03mol sodium carbonate are added in 300mL deionized water, prepares and obtain aqueous slkali B；Constant temperature water bath 65 Under the conditions of DEG C, described saline solution A is mixed with described aqueous slkali B, stir 3～5min, adjusted with 0.2mol/L NaOH solution anti- Answer system pH to 10, continue stirring dynamic crystallization 1h, static ageing 24h, filter, wash, gained filter cake is dried at 70 DEG C, White ZnMgAl-LDHs sample is obtained；
2nd, by step 1 be obtained undried ZnMgAl-LDHs filter cake be distributed to 600mL 0.6g/L enuatrol molten In liquid, with the H of 0.2mol/L at 65 DEG C of constant temperature water bath2SO4Solution adjusts pH value of reaction system to 6, stirs 1h, filters, washs, Gained filter cake is dried at 70 DEG C, modification ZnMgAl-LDHs is obtained, is white powder；
3rd, by Sb2O3Powder is mixed in ball grinder with step 2 gained modification ZnMgAl-LDHs, adds dehydrated alcohol, Rotational speed of ball-mill 400r/min, ratio of grinding media to material 3:Ball milling 8h under conditions of 1, obtains (Sb at 70 DEG C after being dried2O3)15-ZnMgAl-LDHs Composite nanometer flame retardant.Sb2O3The addition of powder is the 5% of modified ZnMgAl-LDHs mass.
Add 5 mass parts (Sb in 100 mass parts PVC2O3)15- ZnMgAl-LDHs composite nanometer flame retardant, preparation obtains Obtain (Sb2O3)15- ZnMgAl-LDHs/ soft pvc nano fire-retarding composite material, and carry out LOI value, UL-94 vertical combustion, rupture and stretch The performance detections such as long rate, tensile strength (are shown in Table 1).Result shows (Sb2O3)15- ZnMgAl-LDHs/ soft pvc nano flame retardant is combined The vertical combustion grade (UL-94) of material reaches V-0 level, and has self-extinguishment；(Sb2O3)15- ZnMgAl-LDHs/ soft pvc hinders The LOI value of composite is improved to 33.4% by 27%, and elongation at break is improved to 168% by 162%, tensile strength by 13.7MPa improves to 14.0MPa, (Sb2O3)15The addition of-ZnMgAl-LDHs fire retardant is less, good flame retardation effect, and to disconnected Split the mechanical impact such as percentage elongation, tensile strength less.

Claims (5)

1. a kind of preparation method of the composite nanometer flame retardant for soft pvc it is characterised in that：Initially with fast nucleation/crystalline substance Change method prepares ZnMgAl-LDHs, then carries out surface modification for modifying agent to ZnMgAl-LDHs with enuatrol, then by Sb2O3Powder Last Yu modified ZnMgAl-LDHs sample mixing and ball milling in ball grinder, obtains Sb2O3The nano combined resistance of-ZnMgAl-LDHs Combustion agent.
2. preparation method according to claim 1 is it is characterised in that comprise the steps：
(1) 0.06mol zinc nitrate and 0.06mol magnesium nitrate are added in 200mL deionized water, prepare and obtain saline solution A；Will 0.06mol sodium aluminate and 0.03mol sodium carbonate add in 300mL deionized water, prepare and obtain aqueous slkali B；65 DEG C of constant temperature water bath Under the conditions of described saline solution A is mixed with described aqueous slkali B, stir 3～5min, adjust pH value of reaction system to 9～11, continue Stirring dynamic crystallization 1h, static ageing 24h, filters, washs, gained filter cake is dried at 70 DEG C, white ZnMgAl-LDHs is obtained Sample；
(2) the undried ZnMgAl-LDHs filter cake that step (1) is obtained is distributed to the Oleic acid of 600mL 0.2～1.2g/L In sodium solution, adjust pH value of reaction system at 65 DEG C of constant temperature water bath to 5～7, stir 1h, filter, wash, gained filter cake is in 70 DEG C Lower drying, is obtained modification ZnMgAl-LDHs, is white powder；
(3) by Sb2O3Powder is mixed in ball grinder with step (2) gained modification ZnMgAl-LDHs, obtains after ball milling drying Sb2O3- ZnMgAl-LDHs composite nanometer flame retardant.
3. preparation method according to claim 2 it is characterised in that：
Described ball milling is wet ball mill, and solvent for use is dehydrated alcohol.
4. preparation method according to claim 2 it is characterised in that：
Rotational speed of ball-mill is 350～650r/min, ratio of grinding media to material 1:1～3:1, Ball-milling Time is 6～14h.
5. preparation method according to claim 2 it is characterised in that：
Sb2O3The addition of powder is Sb2O3The 5～15% of-ZnMgAl-LDHs composite nanometer flame retardant quality.
CN201610723392.3A 2016-08-25 2016-08-25 Preparation method of nano composite flame retardant for soft PVC Pending CN106398020A (en)

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Publication number Priority date Publication date Assignee Title
CN113072745A (en) * 2021-03-20 2021-07-06 合肥工业大学 Preparation method and device of halogen-free composite flame retardant based on modified LDHs

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