CN102492172A - Preparation method and application of nanometer organic-layered composite metal hydroxide - Google Patents
Preparation method and application of nanometer organic-layered composite metal hydroxide Download PDFInfo
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- CN102492172A CN102492172A CN2011104037425A CN201110403742A CN102492172A CN 102492172 A CN102492172 A CN 102492172A CN 2011104037425 A CN2011104037425 A CN 2011104037425A CN 201110403742 A CN201110403742 A CN 201110403742A CN 102492172 A CN102492172 A CN 102492172A
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Abstract
The invention discloses a preparation method and application of nanometer organic-layered composite metal hydroxide. The nanometer organic-inorganic composite layered metal hydroxide is the layered composite metal hydroxide of polymer intercalation compatible with polypropylene and can serve as a synergist to be applied to inflaming retarding combination. The inflaming retarding combination is formed by mixing and compounding the synergist, an organic fire retardant, antioxygen and a lubrication dispersing agent and is especially applicable to flame retarding and enhancing of polypropylene. Compared with the prior art, the prepared nanometer organic-layered composite metal hydroxide has good inflaming retarding, enhancing and toughening effects on a system and can enhance effect with an inflaming retarding composite composed of the nanometer organic-layered composite metal hydroxide mutually, thereby achieving purposes of increasing inflaming retarding temperature and heat absorption capacity and reducing use quantity of the fire retardant.
Description
Technical field
The present invention relates to a kind of nanometer organic-preparation of layered composite metal hydroxides and the application in fire-retardant combination thereof, belong to the engineering plastics technical field.
Background technology
Layered composite metal hydroxides is claimed houghite again, because its stratiform complex hydroxide contains multiple metal hydroxides, just has the advantage of Marinco H and white lake, heat absorption and release water outlet when decomposing, CO concurrently like the magnalium laminar metal hydroxides
2Deng incombustible substance, and can impel the combustible matl carbonization, so it can replace Marinco H and white lake, as polyacrylic fire retardant.But layered composite metal hydroxides is a kind of throw out of high degree of water, has become the chemical bond connection because the dehydration of hydroxyl connects original hydrogen bond during preparation, is prone to produce hard aggregation.Make it be difficult in polymkeric substance, disperseing.Therefore through the organism modification, make its splitting, the preparation nanometer is organic-layered composite metal hydroxides, and it is aligned in polymer melt, improves its flame retardant effect, and can play polymkeric substance is strengthened toughness reinforcing performance.The preparation method who presses down fumicants like the houghite that in publication number CN101280072B, discloses a kind of perfluorinated sulfonate intercalation as polypropylene fire retardant.In publication number CN101845241A, disclose a kind of method of utilizing ultrasonic technology to prepare the intercalation exfoliated hydrotalcite, increased houghite and polyolefinic consistency, but usage quantity has still accounted for 50% of matrix.
Vestolen PP 7052 is one of very important industrial superpolymer; It is low to have production cost; Excellent mechanical property, good insulation performance property, advantage such as nontoxic, corrosion-resistant and density is little; Obtained widespread use in industries such as fields such as chemical industry, chemical fibre, building, light industry, packing, particularly automobile, household electrical appliances, covil construction.But its oxygen index is merely about 17.4%; Charring rate is low, meet the water easy firing, thermal value is high, combustionvelocity is fast; Produce a large amount of molten drops and with the phenomenon of being fuming; Presence of fire has easily limited its Application Areas, is one of focus of current research so develop safe, efficient, eco-friendly PP fire retardant.The fire retardant that is used for Vestolen PP 7052 (PP) at present mainly contains halogen containing flame-retardant, Antimony Trioxide: 99.5Min (Sb
2O
3) Marinco H (Mg (OH)
2), white lake (Al (OH)
3), trimeric cyanamide, ammonium polyphosphate (APP) etc., wherein halogen containing flame-retardant and Sb
2O
3Compound can make PP obtain good flame-retardant effect, but halogen containing flame-retardant discharges a large amount of dense smokes and hydrogen halide when burning, can cause casualties, etching apparatus etc. so-called " secondary disaster ".Sb
2O
3Also exist and increase cigarette, poisonous, dust, shortcoming that price is high, Mg commonly used (OH)
2, Al (OH)
3Deng the addition of inorganic combustion inhibitor big (account for matrix 60%), big to the influence of material, therefore, exploitation Halogen, the environmental protection fire retarding agent that presses down cigarette and do not have a toxic gas are the emphasis of fire-retardant exploitation.
Summary of the invention
The object of the invention provide a kind of nanometer organic-the layered composite metal hydroxides preparation method; Prepared nanometer is organic-and layered composite metal hydroxides can improve the dispersiveness of layered composite metal hydroxides in Vestolen PP 7052; Increase itself and polyacrylic consistency, provide simultaneously this nanometer organic-application of layered composite metal hydroxides in fire-retardant combination; Can make synergy each other between the fire-retardant combination; Improve resistance combustion temperature, increase caloric receptivity, reduce the fire retardant consumption, this fire-retardant combination is particularly suitable for as a kind of Halogen, presses down cigarette and do not have the polypropylene fire retardant agent of toxic gas, is applicable to the preparation acrylic plastering.
To achieve these goals, the technical scheme that the present invention adopted is:
This nanometer is organic-and the preparation method of layered composite metal hydroxides comprises the following steps:
A. compound concentration is the modifier solution of 0.01-0.5 M, and properties-correcting agent is a kind of tensio-active agent that is selected from carboxylate salt that carbonatoms is 12-18, vitriol, the Sulfonates, and heating makes solution temperature be controlled at 60-80 ℃;
B. prepare solubility divalent metal muriate and solubility trivalent metal muriate mixing salt solution, or preparation solubility divalent metal nitrate salt and solubility trivalent metal nitrate salt mixing salt solution, divalence and trivalent metal ion mol ratio 2-4:1;
C. prepare NaOH and Na
2CO
3Mixed ammonium/alkali solutions, wherein the concentration of NaOH is 0.5-2M, Na
2CO
3Concentration be 0.1-0.4M;
D. the solution with the preparation of b step slowly joins in the solution of a step preparation, obtains mixing solutions after the vigorous stirring, and the drips of solution with step c preparation is added in the above-mentioned mixing solutions again, and regulator solution pH value gets colloidal precipitation suspension-s between the 9-11;
E. with the suspension-s of steps d preparation 60-90 ℃ of backflow crystallization 5-30 hour, be washed with water to neutrality after the filtration, under the normal temperature dry 12-36 hour, layered composite metal hydroxides;
F. layered composite metal hydroxides and the maleic anhydride inoculated polypropylene with step e preparation mixes with mixing roll or forcing machine at 160-190 ℃; Extruding pelletization; Both must this nanometer organic-layered composite metal hydroxides, wherein the mass ratio of layered composite metal hydroxides and maleic anhydride inoculated polypropylene is 0.5-0.8:1.
This nanometer is organic-and layered composite metal hydroxides is applied in the fire-retardant combination as synergistic agent; This fire-retardant combination mixes composite forming by synergistic agent with organic fire-retardant, oxidation inhibitor and lubrication dispersing agent; Wherein the weight ratio of each component is a synergistic agent: organic fire-retardant: oxidation inhibitor: lubrication dispersing agent=1-10:10-35:0.05-0.5:0.1-1.0; Described organic fire-retardant is the mixture of ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide; Wherein the weight ratio of each component is an ammonium polyphosphate: tetramethylolmethane: the weight ratio=3-50:1-5:1 of trimeric cyanamide, described oxidation inhibitor are 2,6-di-t-butyl-4-cresols, 2; A kind of among 5-di-tert-butyl hydroquinone, the hydroquinone dibenzyl ether or two kinds, described lubrication dispersing agent is calcium stearate or Zinic stearas or StNa.
Agent is applied in the acrylic plastering said fire-retardant combination as polypropylene fire retardant.
Compared with prior art, advantage of the present invention is:
The nanometer of preparation organic-layered metal hydroxides is peeled off effectively, can promptly in melt polypropylene, align, and shows tangible anisotropy, system is played good flame and strengthens toughening effect;
With organic fire-retardant and nanometer organic-layered metal hydroxides is composite, the fire-retardant combination of processing can the mutual synergy of-layered metal hydroxides organic with nanometer, reaches the raising resistance combustion temperature, increases caloric receptivity, reduces the purpose of fire retardant consumption;
3. the fire-retardant combination of preparation is a kind of Halogen, presses down cigarette and do not have the environment friendly flame retardant of toxic gas.
Embodiment
Below in conjunction with embodiment to the detailed description of the invention.
Embodiment 1: and nanometer is organic-and layered composite metal hydroxides is as the preparation of synergistic agent
Get 14.4g (0.05mol) sodium lauryl sulphate and be dissolved in the 150ml water, be heated to 70 ℃ (being designated as solution 1).Get the solid MgCl of 3.05g (0.015mol)
26H
2O and 1.2g (0.005mol) AlCl
36H
2O is dissolved in the 45ml water and (is designated as solution 2).Get NaOH and 1.06g (0.01mol) NaCO of 2.1g (0.05mol)
3Be dissolved in the 54ml water and (be designated as solution 3).Solution 2 and solution 3 dropwise are added in the solution 3 simultaneously, and the speed of regulating both dropwises simultaneously, regulates pH to 10 with the NaOH solution of 2M then, gets colloidal precipitation.With colloidal precipitation in 70 ℃ aging 24 hours, suction filtration is washed with water to pH value less than 8,80 ℃ of dryings 24 hours, must layered composite metal hydroxides.
The layered composite metal hydroxides and the maleic anhydride inoculated polypropylene (commercially available) of preparation are mixed at forcing machine with 1:1 weight part ratio; (screw speed is 100rpm to extruding pelletization; Extrusion temperature is controlled to be 180 ℃), nanometer organic-layered composite metal hydroxides.
Embodiment 2: and nanometer is organic-and layered composite metal hydroxides is as the preparation of synergistic agent
Get 25g (0.075mol) StNa and be dissolved in the 150ml water, be heated to 80 ℃ (being designated as solution 1).Get the solid MgCl of 1.02g (0.005mol)
26H
2O, 1.37gZnCl
2(0.01mol) and 1.34g (0.005mol) CrCl
36H
2O is dissolved in the 45ml water and (is designated as solution 2).Get NaOH and 1.06g (0.01mol) NaCO of 2.1g (0.05mol)
3Be dissolved in the 54ml water and (be designated as solution 3).Solution 2 and solution 3 dropwise are added in the solution 3 simultaneously, and the speed of regulating both dropwises simultaneously, regulates pH to 10 with the NaOH solution of 2M then, gets colloidal precipitation.With colloidal precipitation in 80 ℃ aging 24 hours, suction filtration is washed with water to pH value less than 8,80 ℃ of dryings 24 hours, must layered composite metal hydroxides.
The layered composite metal hydroxides and the maleic anhydride inoculated polypropylene (commercially available) of preparation are mixed at forcing machine with 1:1 weight part ratio; (screw speed is 100rpm to extruding pelletization; Extrusion temperature is controlled to be 180 ℃), nanometer organic-layered composite metal hydroxides.
Embodiment 3-7: the weight ratio content of each component (form below seeing for details) in acrylic plastering
| Embodiment | PP | Organic fire-retardant | Synergistic agent | Oxidation inhibitor | Lubrication dispersing agent | Oxygen index (LOI%) | Flame retardant properties |
| 3 | 75 | 25 | 0 | 0.2 | 0.5 | 23.7 | V-0 |
| 4 | 73 | 25 | 2 | 0.2 | 0.5 | 26.1 | V-0 |
| 5 | 71 | 25 | 4 | 0.2 | 0.5 | 27.4 | V-0 |
| 6 | 69 | 25 | 6 | 0.2 | 0.5 | 26.2 | V-0 |
| 7 | 67 | 25 | 8 | 0.2 | 0.5 | 25.3 | V-0 |
In the top form; Vestolen PP 7052 adopts the HOPP of Korea S's import; Synergistic agent be the nanometer of preparation among the embodiment 1 organic-layered composite metal hydroxides, organic fire-retardant is ammonium polyphosphate (APP): tetramethylolmethane (PER): the mixture of trimeric cyanamide (MEL)=4:2:1 (weight ratio), oxidation inhibitor adopt 2; 6-di-t-butyl-4-cresols; Lubrication dispersing agent adopts calcium stearate, and wherein synergistic agent mixes composite composition fire-retardant combination with organic fire-retardant, oxidation inhibitor and lubrication dispersing agent, and this fire-retardant combination can be used as the polypropylene fire retardant agent.
Embodiment 3 is not when adding synergistic agent; Vestolen PP 7052 and organic fire-retardant, oxidation inhibitor and lubrication dispersing agent are as the component of acrylic plastering; Flame retardant properties (UL-94) is V-0; Embodiment 4-7 is Vestolen PP 7052 and this fire-retardant combination component as acrylic plastering, and flame retardant properties (UL-94) is V-0, the oxygen index of the oxygen index of acrylic plastering when adding synergistic agent when not adding synergistic agent.
Embodiment 8-12: the weight ratio content of each component (form below seeing for details) in acrylic plastering
| Embodiment | PP | Organic fire-retardant | Synergistic agent | Oxidation inhibitor | Lubrication dispersing agent | Oxygen index (LOI%) | Flame retardant properties |
| 8 | 80 | 20 | 0 | 0.2 | 0.5 | 23.4 | V-0 |
| 9 | 78 | 20 | 2 | 0.2 | 0.5 | 25.9 | V-0 |
| 10 | 76 | 20 | 4 | 0.2 | 0.5 | 26.9 | V-0 |
| 11 | 74 | 20 | 6 | 0.2 | 0.5 | 25.2 | V-0 |
| 12 | 72 | 20 | 8 | 0.2 | 0.5 | 25.0 | V-0 |
In the top form, Vestolen PP 7052 adopts the HOPP of Korea S's import, synergistic agent be the nanometer for preparing among the embodiment 2 organic-layered composite metal hydroxides; Organic fire-retardant is the mixture of APP:PER:MEL=4:2:1 (weight ratio); Oxidation inhibitor adopts 2,6-di-t-butyl-4-cresols, and lubrication dispersing agent adopts calcium stearate; Wherein synergistic agent mixes composite composition fire-retardant combination with organic fire-retardant, oxidation inhibitor and lubrication dispersing agent, and this fire-retardant combination can be used as the polypropylene fire retardant agent.
Embodiment 8 is not when adding synergistic agent; Vestolen PP 7052 and organic fire-retardant, oxidation inhibitor and lubrication dispersing agent are as the component of acrylic plastering; Flame retardant properties (UL-94) is V-I; Embodiment 9-12 is Vestolen PP 7052 and this fire-retardant combination component as acrylic plastering, and flame retardant properties (UL-94) is V-0, the oxygen index of acrylic plastering when adding synergistic agent oxygen index when not adding synergistic agent.
Claims (3)
- A nanometer organic-preparation method of layered composite metal hydroxides, it is characterized in that comprising the following steps:A. compound concentration is the modifier solution of 0.01-0.5 M, and properties-correcting agent is a kind of tensio-active agent that is selected from carboxylate salt that carbonatoms is 12-18, vitriol, the Sulfonates, and heating makes solution temperature be controlled at 60-80 ℃;B. prepare solubility divalent metal muriate and solubility trivalent metal muriate mixing salt solution, or preparation solubility divalent metal nitrate salt and solubility trivalent metal nitrate salt mixing salt solution, divalence and trivalent metal ion mol ratio 2-4:1;C. prepare NaOH and Na 2CO 3Mixed ammonium/alkali solutions, wherein the concentration of NaOH is 0.5-2M, Na 2CO 3Concentration be 0.1-0.4M;D. the solution with the preparation of b step slowly joins in the solution of a step preparation, obtains mixing solutions after the vigorous stirring, and the drips of solution with step c preparation is added in the above-mentioned mixing solutions again, and regulator solution pH value gets colloidal precipitation suspension-s between the 9-11;E. with the suspension-s of steps d preparation 60-90 ℃ of backflow crystallization 5-30 hour, be washed with water to neutrality after the filtration, at 80 ℃ of dry 12-36 hours, layered composite metal hydroxides;F. layered composite metal hydroxides and the maleic anhydride inoculated polypropylene with step e preparation mixes with mixing roll or forcing machine at 160-190 ℃; Extruding pelletization; Both must this nanometer organic-layered composite metal hydroxides, wherein the mass ratio of layered composite metal hydroxides and maleic anhydride inoculated polypropylene is 0.5-0.8:1.
- One kind as the prepared nanometer of claim 1 organic-application of layered composite metal hydroxides; It is characterized in that: this nanometer is organic-and layered composite metal hydroxides is applied in the fire-retardant combination as synergistic agent; This fire-retardant combination mixes composite forming by synergistic agent with organic fire-retardant, oxidation inhibitor and lubrication dispersing agent; Wherein the weight ratio of each component is a synergistic agent: organic fire-retardant: oxidation inhibitor: lubrication dispersing agent=1-10:10-35:0.05-0.5:0.1-1.0; Described organic fire-retardant is the mixture of ammonium polyphosphate, tetramethylolmethane and trimeric cyanamide; Wherein the weight ratio of each component is an ammonium polyphosphate: tetramethylolmethane: the weight ratio=3-50:1-5:1 of trimeric cyanamide, described oxidation inhibitor are 2,6-di-t-butyl-4-cresols, 2; A kind of among 5-di-tert-butyl hydroquinone, the hydroquinone dibenzyl ether or two kinds, described lubrication dispersing agent is calcium stearate or Zinic stearas or StNa.
- 3. nanometer according to claim 2 is organic-application of layered composite metal hydroxides, and it is characterized in that: agent is applied in the acrylic plastering said fire-retardant combination as polypropylene fire retardant.
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Cited By (6)
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| CN103351524A (en) * | 2013-08-09 | 2013-10-16 | 中国日用化学工业研究院 | Preparation method of modified nanometer magnesium-aluminum composite fire retardant |
| CN103613845A (en) * | 2013-11-21 | 2014-03-05 | 浙江大学宁波理工学院 | Flame retardant polypropylene composite compounded by layered thermometal hydroxide and intumescent flame retardant and preparation method of flame retardant polypropylene composite |
| CN105175776A (en) * | 2015-10-26 | 2015-12-23 | 厦门理工学院 | Nanometer halogen-free flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
| CN107199610A (en) * | 2017-05-18 | 2017-09-26 | 阜南县星光工艺品有限公司 | A kind of method for improving Manchurian ash timber anti-flammability |
| CN108299799A (en) * | 2018-01-27 | 2018-07-20 | 浙江大学 | The layered double hydroxide and its preparation method and application that cagelike silsesquioxane is modified |
| CN109914117A (en) * | 2019-04-04 | 2019-06-21 | 厦门鑫创利硅胶有限公司 | A kind of flame-retardant leather, preparation method and application |
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| CN105175776A (en) * | 2015-10-26 | 2015-12-23 | 厦门理工学院 | Nanometer halogen-free flame-retardant thermoplastic polyurethane elastomer and preparation method thereof |
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| CN107199610A (en) * | 2017-05-18 | 2017-09-26 | 阜南县星光工艺品有限公司 | A kind of method for improving Manchurian ash timber anti-flammability |
| CN108299799A (en) * | 2018-01-27 | 2018-07-20 | 浙江大学 | The layered double hydroxide and its preparation method and application that cagelike silsesquioxane is modified |
| CN108299799B (en) * | 2018-01-27 | 2019-09-20 | 浙江大学 | The modified layered double hydroxide and its preparation method and application of cagelike silsesquioxane |
| CN109914117A (en) * | 2019-04-04 | 2019-06-21 | 厦门鑫创利硅胶有限公司 | A kind of flame-retardant leather, preparation method and application |
| CN109914117B (en) * | 2019-04-04 | 2021-07-13 | 厦门鑫创利硅胶有限公司 | Flame-retardant leather, preparation method and application |
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Application publication date: 20120613 |