CN101280072B - Hydrotalcite-like compound as flame-retardant smoke-suppressant agent for engineering plastics and preparation thereof - Google Patents
Hydrotalcite-like compound as flame-retardant smoke-suppressant agent for engineering plastics and preparation thereof Download PDFInfo
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- CN101280072B CN101280072B CN2008101050835A CN200810105083A CN101280072B CN 101280072 B CN101280072 B CN 101280072B CN 2008101050835 A CN2008101050835 A CN 2008101050835A CN 200810105083 A CN200810105083 A CN 200810105083A CN 101280072 B CN101280072 B CN 101280072B
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Abstract
A hydrotalcite-like compound used as flame retardant and smoke suppressant of engineering plastics and the preparation method of the hydrotalcite-like compound belong to the technical field of catalytic materials. The chemical formula of the flame retardant and smoke suppressant is as follows: Mg2Al(OH)6*C4F9SO3*mH2O or ZnMgAl(OH)6*C4F9SO3*mH2O. First of all, layered double hydroxide precursors with particle size of nano or sub-micron level are prepared through common preparation methods of hydrotalcite-like materials, such as co-precipitation, crystal nucleation/isolation, non-equilibrium crystallization or hydrothermal synthesis; then different intercalation products are prepared through adjusting the number of anions; finally, the flame retarding and smoke suppressing performances of the hydrotalcite-like compound to ABS and PP are tested by changing the adding amount of the intercalation products. The hydrotalcite-like compound of the invention has the advantages of simple and easypreparation method and good effects, which is suitable for industrial production.
Description
Technical field
The invention belongs to the engineering plastics technical field, particularly relate to a kind of hydrotalcite-like compound as flame-retardant smoke-suppressant agent for engineering plastics and preparation method thereof, be that the organic anion intercalated houghite is used as flame-retardant smoke-suppressant agent for engineering plastics and preparation method thereof, be specifically related to the intercalation method of a kind of nano level and micron order layered di-hydroxyl composite metal oxidate.This intercalation product is applicable to engineering plastics and general-purpose plastics as anti-flaming smoke-inhibiting agent, is particularly useful for acrylonitrile-butadiene-styrene copolymer (being called for short ABS) resin and polypropylene (being called for short PP) plastics.
Background technology
The terpolymer that ABS resin is made up of vinyl cyanide, divinyl and vinylbenzene, has good rigidly, shock strength height, heat-resisting, low temperature resistant, chemical proofing, physical strength and electric property are good, be easy to processing, finish size stability and surface luster are good, easily application, painted, can also carry out metallize, plating, welding and suitability for secondary processing such as bonding.Have a wide range of applications in industries such as automobile, utensil, electronics, electrical equipment, building materials.But ABS belongs to inflammable material, and this has limited its application to a certain extent.Therefore the research of flame-proof ABS has also just had considerable meaning.
The fire-retardant research of ABS: the fire retardant that is used for ABS mainly contains phosphorus system, halogen is organism and some mineral compound, wherein inorganic combustion inhibitor addition in ABS need reach just has more than 40% than obvious effects, big owing to its addition simultaneously, so the physical and mechanical property of meeting grievous injury ABS.And phosphorus flame retardant kind, comparatively small amt, and majority is again liquid and low melting component, is not suitable for the granulation complete processing of ABS.Therefore, current flame-retardant system for ABS mainly adopts halogenated flame retardant, as decabromodiphenyl oxide (DBDPO), tetrabromo-bisphenol etc.The low fuming research of ABS: in the research of flame-proof ABS, though adopt the fire retardant addition of bromine class few, good flame retardation effect, over-emitting black exhaust when burning, and the dust of many black is arranged, environment is brought serious pollution.Therefore, press for ABS is further studied with fire retardant.
Polypropylene (PP) is a kind of general-purpose plastics, as one of three big plastics, has characteristics such as excellent mechanical property, good insulation performance, chemical proofing and density are little and is widely used in industries such as automobile, household electrical appliances, weaving, building.Yet reason owing to the PP self structure, oxygen index only is about 17.4, meet fiery easy firing, thermal value height, combustionvelocity fast, produce a large amount of molten drops and with the phenomenon of being fuming, presence of fire easily, flame propagation speed, be difficult for extinguishing, cause great injury for people's life, property, its Application Areas is subjected to great restriction.Therefore, PP flame-retardant modified become a research focus.
The fire retardant that is used for PP at present mainly contains magnesium hydroxide, ZnO, trimeric cyanamide, APP etc., and wherein the addition of inorganic combustion inhibitor is big, and is big to the mechanical property influence.Organic fire-retardant: give off poisonous gas, produce smog; Produce corrosives; Environmental pollution is serious.Therefore, need the new environmental protection fire retarding agent of exploitation.
Hydrotalcite-based compound comprises hydrotalcite (Hydrotalcite) and houghite (Hydrotalcite-likecompound), its main body generally is made of the oxyhydroxide of two kinds of metals, therefore be called layered di-hydroxyl composite metal oxidate (Layered Double Hydroxide is abbreviated as LDH) again.The intercalation compound of LDH is called intercalated houghite.Hydrotalcite, houghite and intercalated houghite are referred to as hydrotalcite intercalation material (LDHs).Such material is a kind of inorganic materials with unique structural characteristics: having established this class material as the Modulatory character of elementary composition adjustable sex change, grain-size and distribution in relative broad range and the designability of interlayer intercalant anion kind etc. might become the fire retardant with potential application foreground or the basis of fire retardant presoma.
Because special structure and composition absorbs big calorimetric during the LDHs decomposes, decompose the water and the carbon dioxide gas physical efficiency that discharge and dilute, intercept inflammable gas; Product after the decomposition is alkaline porous material, and specific surface is big, can adsorb particularly sour gas of obnoxious flavour.Thereby have the flame-retardant smoke inhibition dual-use function, can be used as fire retardant and be applied to polymeric material field.
LDHs is used for PVC and fills to improve the PVC performance and report the earliest and see the seventies (repair in following village, and high well is good male, damp Tian Zhengshi; Japan go system association will, 1976,49 (1): 35), discover that the LDHs filled PVC shows the high oxygen index identical with Al (OH) 3 and it has the stronger receptivity to HCl.Another piece patent report (Feng Tao, high structure control and the performance study that presses down cigarette Halogen inorganic nano fire retardant of LDHs base, Beijing University of Chemical Technology's master thesis, 2003.3), 100 parts of PVC, 50 parts of di(2-ethylhexyl)phosphate phenyl octyl group esters, the material that 1 part of LDHs and other metal-salt constitute, its oxygen index reaches 23.3%, and has significant smoke effect.This laboratory is added to LDHs among the PVC as fire retardant, investigate its flame retardant effect (Huang Baosheng to plastic material, the preparation of nano double hydroxy composite metal oxide and the research of the application performance in PVC thereof, Beijing University of Chemical Technology's master thesis, 2001.5), found that its less addition (20phr) just can significantly improve smoke suppressing effect when not reducing the material oxygen index.Fire retardation and the mechanism (Zhao Yun of LDHs to Resins, epoxy also studied in this laboratory, the controlled preparation and the applied research of layered double hydroxide and oxide compound, Beijing University of Chemical Technology's doctorate paper, 2002.4), the result shows that it has significant smoke suppressing effect, and fire retardation is deferred to the fire-retardant and condensed phase fire retardant mechanism of gas phase.It is reported, in the world because of the dead philtrum of fire failure, be because the smog and the poisonous gas that give out in the macromolecular material burning are choked to death the people more than 90%, is not that naked light burns body.Just because of this, the aflame cigarette problem that presses down of macromolecular material more and more obtains people's attention, and becomes inevitable problem in the fire-retardant research.The high smoke-suppressing of LDHs is expected to address this problem.Fire-retardant report (the Jiang Zhijie etc. of relevant perfluoro butyl potassium sulfonate, the research of perfluoro butyl potassium sulfonate fire retardation PC kinetics of thermal decomposition, 2007.1), to be 0.01% oxygen index that can make PC bring up to 35% from 26% to the addition of perfluoro butyl potassium sulfonate, and addition is 0.1% can make the PC oxygen index reach 39%.
In above-mentioned document, the houghite material has shown good flame-retardant effect as fire retardant, still, the addition that such material is bigger in use, this has brought adverse influence for the machinery and the mechanical property of macromolecular material.Simultaneously the perfluoro butyl potassium sulfonate is a fire retardant very efficiently, and again according to the structure designability of houghite material, expectation is inserted hydrotalcite layers with the perfluoro butyl sulfonate radical and can be obtained better flame-retardant smoke inhibition effect and reduce its addition simultaneously.
Summary of the invention
The purpose of this invention is to provide hydrotalcite-like compound as flame-retardant smoke-suppressant agent for engineering plastics and preparation method thereof, solved the preparation of organic anion intercalated houghite and the flame-retardant smoke inhibition problem of engineering plastics.
The preparation method of organic anion intercalated houghite provided by the invention is: realize that first the perfluoro butyl sulfonate radical that will have better flame retardant resistance is inserted into hydrotalcite layers.Promptly at first utilize methods such as common houghite preparation methods such as coprecipitation method, nucleation crystallization/isolation method, non-equilibrium crystallization method or hydro-thermal be synthetic to prepare layered di-hydroxyl composite metal oxidate (houghite) precursor of particle diameter for nano level or submicron order, then by the anionic quantity of modulation, prepare different intercalation products, the addition that changes the intercalation product is at last again investigated its flame-proof smoke-suppressing to ABS and PP.
Layered di-hydroxyl composite metal oxidate fire retardant provided by the invention, its chemical formula is:
Mg
2Al (OH)
6C
4F
9SO
3MH
2O or ZnMgAl (OH)
6C
4F
9SO
3MH
2O
M is a crystal water quantity, and span is 0.5～9.
Concrete preparation process of the present invention is as follows:
At first utilize methods such as common houghite preparation methods such as coprecipitation method, nucleation crystallization/isolation method, non-equilibrium crystallization method or hydro-thermal be synthetic to prepare layered di-hydroxyl composite metal oxidate (houghite) precursor of particle diameter for nano level or submicron order, then by the anionic quantity of modulation, prepare different intercalation products, the addition that changes the intercalation product is at last again investigated its flame-proof smoke-suppressing to ABS and PP.
The invention is characterized in:
A: the Mg (NO of the 0.01～2.00mol/1 that will prepare
3)
26H
2O and Al (NO
3)
39H
2O salts solution or Mg (NO
3)
26H
2O, Zn (NO
3)
26H
2O and Al (NO
3)
39H
2The NaOH alkaline solution of O salts solution and 0.01～4.0mol/l adds reactor simultaneously, the houghite colloidal substances do that will prepare but handle without super-dry spends the carbonic acid gas water washing, the pH value that makes supernatant liquor is 7～8, add that to be made into solid content (the quality percentage composition of solid matter in the slurries) after going carbonic acid gas water to stir be 1%～50% slurries, regulating the pH value is 6～10 again;
Used houghite materials chemistry general formula is: [M
21-xM
3+ x (OH)
2]
X+(An-)
X/nMH
2O
Wherein, M
2+Be Mg
2+Or Mg
2+With Zn
2+M
3+Be Al
3+M is a crystal water quantity, and span is 0.5～9.
B: adding molar weight in the houghite slurries of steps A is 0.1～5.0 times perfluoro butyl potassium sulfonate of solid content (the quality percentage composition of solid matter in the slurries), stirring makes system be even colloidal state shape, keep 50～100 ℃ of reactions 2～48 hours down in nitrogen protection, colloidal state obtains slurries;
C: the colloidal state slurries of step B are washed with water, and the pH value that makes supernatant liquor is 7～8,50～180 ℃ of dryings, obtains product.
D: take by weighing mass ratio with ABS or PP and be the product of 1%～100% step C gained and ABS or PP and mix with muller or forcing machine, use the sample preparation of tabletting machine compressing tablet again at 160～190 ℃.
Adopt Shimadu XR9-6000 type powder x-ray diffraction that the product of preparation is carried out qualitative analysis, the result is as follows:
The XRD spectra of the hydrotalcite precursor that Fig. 1 is obtained for embodiment 1,2, from figure as can be seen, the characteristic peak (003) that 3 diffracted intensities of hydrotalcite are bigger, (006) and (009) appear at 9.84 °, 19.78 ° and 29.78 ° respectively and locate, the interlamellar spacing d of (003) diffraction peak correspondence of reflection interlamellar spacing
003Value is 0.90nm, and the diffractogram baseline hangs down flat and each diffraction peak peak shape point is alarmmed, and synthetic MgAl-NO is described
3-LDHs precursor has complete laminate structure.
The XRD spectra of the intercalation product that Fig. 2 is obtained for embodiment 1,2, insert the interlayer of MgAl-NO3-LDHs precursor when the PFB negatively charged ion after, identical with the phenomenon that is showed between other bigger negatively charged ion insertions LDHs precursor layer, new (003), (006) and (009) diffraction peak appear at 4.18 °, 8.64 ° and 12.58 ° respectively and locate, at this moment d
003Corresponding interlamellar spacing is 2.11nm, and this shows that the PFB negatively charged ion has entered interlayer replacement NO3-and formed MgAl-PFB-LDHs, and has kept laminate structure preferably.
Adopt VECTOR22 type FT-IR to measure the structure of compound, the result is as follows:
Fig. 3 is the hydrotalcite precursor intercalation product of embodiment 3 gained and the infrared spectrum of intercalation object, from a figure as can be seen at 1384cm
-1NO has appearred in the place
3 -The feature stretching vibration peak and at 450cm
-1The place occur one with the LDHs laminate on the relevant vibration peak of O-M-O key; From the b figure as can be seen at 1261cm
-1The place has occurred-SO3
-The charateristic avsorption band of group; From the c figure as can be seen after object PFB inserts between precursor layer ,-SO3
-The charateristic avsorption band of group has moved on to 1257cm
-1The place is originally at 1384cm
-1The NO of place
3 -Absorption peak disappear, and equally at 448cm
-1O-M-O vibration peak, 3450cm have appearred in the place
-1About the stretching vibration absorption peak of laminate hydroxyl O-H and middle water appears, this shows that the PFB negatively charged ion replaces NO fully in the intercalation product
3 -Enter the LDHs interlayer.
Adopt JF-3 type limiting oxygen index determination instrument to carry out the oxygen index test according to standard GB/T2406, the result is as follows:
Table 1 is the measured oxygen index value of example 1,2;
Table 2 is the measured oxygen index value of example 3,4;
Adopt JCY-1 type smoke density tester to carry out the smoke density test according to standard GB/T8627-1999, the result is as follows:
Table 3 is the measured smoke density values of example 1,2;
Table 4 is the measured smoke density value of example 3,4;
Distinguishing feature of the present invention is the intercalation by means of hydrotalcite, and the perfluoro butyl sulfonate radical that will have better flame retardant resistance is inserted into hydrotalcite layers.Adopt method provided by the invention to prepare the layered di-hydroxyl composite metal oxidate fire retardant, its preparation method is easy, and is respond well, suitability for industrialized production.
Description of drawings
Fig. 1 is the XRD spectra of the hydrotalcite precursor that obtained of embodiment 1,2;
Fig. 2 is the XRD spectra of the hydrotalcite intercalation product that obtained of embodiment 1;
Fig. 3 is the FT-IR spectrogram that embodiment 3 is obtained;
Embodiment
The invention will be further described below in conjunction with embodiment:
Example 1
A: take by weighing 71.79g Mg (NO
3)
26H
2O and 52.52g Al (NO
3)
39H
2O is dissolved in and is made into the 350mL mixing salt solution in the carbonic acid gas water; And then take by weighing 26.88g NaOH and be dissolved in and be made into the 350mL mixed ammonium/alkali solutions in the carbonic acid gas water; Above-mentioned two kinds of mixing solutionss are added full back-mixing liquid film reactor simultaneously, slit width between conditioned reaction device rotor and the stator is 2mm, operating voltage is 140V, rotor speed is 5000rpm, the mixed serum that obtains is added heated and stirred in the there-necked flask, nitrogen protection, keeping the temperature of bottle mixed serum is 80 ℃ of backflow crystallization 6 hours, obtains magnesia-alumina hydrotalcite precursor;
B: the product of steps A preparation is spent carbonic acid gas water thorough washing, the pH value that makes the liquid that disappears is 7, add again that to be made into solid content after carbonic acid gas water fully stirs be 5% slurries, regulating the pH value is 7, add heated and stirred in the there-necked flask, nitrogen protection allows the temperature of mixed serum reaches 80 ℃ in the bottle;
C: add and the equimolar perfluoro butyl potassium sulfonate of solid content in the houghite slurries of step B, fully stirring makes system be even colloidal state shape, keeps 80 ℃ of reactions 6 hours down in nitrogen protection, obtains magnesia-alumina hydrotalcite intercalation product;
D: the colloidal state slurries of step C are spent carbonic acid gas water thorough washing, and the pH that makes supernatant liquor was 7, in 70 ℃ of dryings 12 hours.
E: take by weighing the sample of 1g step D gained, take by weighing 100gABS again, 170 ℃ mix on the two-wheel muller, with the sample preparation of vulcanizing press compressing tablet, last test oxygen index and smoke density.
Example 2
A: with example 1;
B: with example 1;
C: with example 1;
D: with example 1;
E: take by weighing the sample of 100g step D gained, take by weighing 100gABS again, 170 ℃ mix on the two-wheel muller, with the sample preparation of vulcanizing press compressing tablet, last test oxygen index and smoke density.
Example 3
A: take by weighing 23.80g Zn (NO
3)
26H
2O, 20.51g Mg (NO
3)
26H
2O and 30.01g Al (NO
3)
39H
2O is dissolved in and is made into the 200mL mixing salt solution in the carbonic acid gas water; And then take by weighing 15.36g NaOH and be dissolved in and be made into the 200mL mixed ammonium/alkali solutions in the carbonic acid gas water; Above-mentioned two kinds of mixing solutionss are added full back-mixing liquid film reactor simultaneously, slit width between conditioned reaction device rotor and the stator is 2mm, operating voltage is 140V, rotor speed is 5000rpm, the mixed serum that obtains is added heated and stirred in the there-necked flask, nitrogen protection, keeping the temperature of bottle mixed serum is 80 ℃ of backflow crystallization 6 hours, obtains zinc-magnesium aluminium houghite precursor;
B: the product of steps A preparation is spent carbonic acid gas water thorough washing, the pH value that makes supernatant liquor is 7, add again that to be made into solid content after carbonic acid gas water fully stirs be 5% slurries, regulating the pH value is 7, add heated and stirred in the there-necked flask, nitrogen protection allows the temperature of mixed serum reaches 80 ℃ in the bottle;
C: add and the equimolar perfluoro butyl potassium sulfonate of solid content in the houghite slurries of step B, fully stirring makes system be even colloidal state shape, keeps 80 ℃ of reactions 6 hours down in nitrogen protection, obtains zinc-magnesium aluminium houghite intercalation product;
D: the colloidal state slurries of step C are spent carbonic acid gas water thorough washing, and the pH value that makes supernatant liquor was 7, in 70 ℃ of dryings 12 hours.
E: take by weighing the sample of 1g step D gained, take by weighing 100gPP again, 160 ℃ mix on the two-wheel muller, with the sample preparation of vulcanizing press compressing tablet, last test oxygen index and smoke density.
Example 4
A: with embodiment 3;
B: with embodiment 3;
C: with embodiment 3;
D: with embodiment 3;
E: take by weighing the sample of 100g step D gained, take by weighing 100gPP again, 160 ℃ mix on the two-wheel muller, with the sample preparation of vulcanizing press compressing tablet, last test oxygen index and smoke density.
The oxygen index test data that table 1: embodiment 1,2 is obtained
| Sample | Addition/part | Oxygen index (%) |
| ABS | 0 | 17.7 |
| MgAl-PFB-LDHs | 1 | 18.3 |
| MgAl-PFB-LDHs | 100 | 32.4 |
The oxygen index test data that table 2: embodiment 3,4 is obtained
| Sample | Addition/part | Oxygen index (%) |
| PP | 0 | 17.8 |
| Sample | Addition/part | Oxygen index (%) |
| ZnMgAl-PFB-LDHs | 1 | 18.5 |
| ZnMgAl-PFB-LDHs | 100 | 32.1 |
The smoke density test data that table 3: embodiment 1,2 is obtained
| Sample | Addition/part | Smoke density (%) |
| ABS | 0 | 98.96 |
| MgAl-PFB-LDHs | 1 | 96.56 |
| MgAl-PFB-LDHs | 100 | 46.36 |
The smoke density test data that table 4: embodiment 3,4 is obtained
| Sample | Addition/part | Smoke density (%) |
| PP | 0 | 41.24 |
| ZnMgAl-PFB-LDHs | 1 | 39.39 |
| ZnMgAl-PFB-LDHs | 100 | 20.53 |
Claims (2)
1. a hydrotalcite-like compound as flame-retardant smoke-suppressant agent for engineering plastics is characterized in that, chemical formula is: Mg
2Al (OH)
6C
4F
9SO
3MH
2O or ZnMgAl (OH)
6C
4F
9SO
3MH
2O, m are crystal water quantity, and span is 0.5～9.
2. a method for preparing the described anti-flaming smoke-inhibiting agent of claim 1 is characterized in that, technology is:
Mg (the NO of A, the 0.01～2.00mol/l that will prepare
3)
26H
2O and Al (NO
3)
39H
2O salts solution or Mg (NO
3)
26H
2O, Zn (NO
3)
26H
2O and Al (NO
3)
39H
2The NaOH alkaline solution of O salts solution and 0.01～4.0mol/l adds reactor simultaneously, the houghite colloidal substances do that will prepare but handle without super-dry spends the carbonic acid gas water washing, the pH value that makes supernatant liquor is 7～8, add that to be made into solid content after going carbonic acid gas water to stir be 1%～50% slurries, regulating the pH value is 6～10 again; Used houghite materials chemistry general formula is: [M
2+ 1-xM
3+ x(OH)
2]
X+(A
N-)
X/nMH
2O, wherein, M
2+Be Mg
2+Or Mg
2+With Zn
2+M
3+Be Al
3+Described solid content is the quality percentage composition of solid matter in the slurries; M is a crystal water quantity, and span is 0.5～9;
B, to add molar weight in the houghite slurries of steps A be 0.1～5.0 times perfluoro butyl potassium sulfonate of solid content, stirs to make system be even colloidal state shape, keeps 50～100 ℃ of reactions 2～48 hours down in nitrogen protection, obtains the colloidal state slurries;
C, the colloidal state slurries of step B are washed with water, the pH value that makes supernatant liquor is 7～8,50～180 ℃ of dryings, obtains product;
D, take by weighing with acrylonitrile-butadiene-styrene copolymer resin or polyacrylic mass ratio be that the product of 1%～100% step C gained and acrylonitrile-butadiene-styrene copolymer resin or polypropylene mix with muller or forcing machine at 160～190 ℃, use the sample preparation of tabletting machine compressing tablet again.
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| CN101544815B (en) * | 2009-04-14 | 2011-04-27 | 桂林工学院 | A preparing method for unsaturated polyester resins flame-retardant composite material |
| CN101538411B (en) * | 2009-04-17 | 2011-06-01 | 北京化工大学 | Catalysis carbon-forming type flame-retardant composite material and preparation method thereof |
| CN102702572B (en) * | 2012-06-05 | 2014-01-22 | 湖北鑫海新材料科技有限公司 | Gradient inflaming retarding material of hydrotalcite-like nano calcium carbonate prepared by natural dolomite and preparation method thereof |
| CN103509309A (en) * | 2012-06-27 | 2014-01-15 | 合肥杰事杰新材料股份有限公司 | Environment-friendly low-smoke fire-retardant acrylonitrile-butadiene-styrene (ABS) resin and preparation method thereof |
| CN105237808B (en) * | 2015-10-08 | 2018-06-01 | 中国科学院长春应用化学研究所 | Intercalation composite material and preparation method thereof, polymer nanocomposites |
| CN106084852A (en) * | 2016-08-05 | 2016-11-09 | 宁波金特信钢铁科技有限公司 | A kind of preparation method of automobile-used biological engineering plastics |
| CN108659514B (en) * | 2018-06-02 | 2020-11-03 | 北京化工大学 | Preparation and application of polyurethane efficient smoke suppressant |
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