CN101824200B - Dendritic flame-retardant layered silicate and preparation method thereof - Google Patents
Dendritic flame-retardant layered silicate and preparation method thereof Download PDFInfo
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- CN101824200B CN101824200B CN2010100228842A CN201010022884A CN101824200B CN 101824200 B CN101824200 B CN 101824200B CN 2010100228842 A CN2010100228842 A CN 2010100228842A CN 201010022884 A CN201010022884 A CN 201010022884A CN 101824200 B CN101824200 B CN 101824200B
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Abstract
The invention discloses dendritic flame-retardant layered silicate and a preparation method thereof, and the preparation method comprises the following steps: (1) mixing inorganic montmorillonite and high heat-resistant organic intercalator, adding ethanol water solution, stirring for 2-4h at 75-80DEG C and collecting high heat-resistant organic montmorillonite; (2) stirring the high heat-resistant organic montmorillonite, putrescine, acrylonitrile and catalyst for 5-8h at 70-90DEG C, and then collecting dendritic organic montmorillonite from the product; and (3) stirring the dendritic organic montmorillonite and alpha-(diphenylphosphino) acetic acid for 1-2h at 60-80DEG C, then adding zinc borate, and stirring for 2-4h at 70-90DEG C, thus obtaining the dendritic flame-retardant layered silicate. The dendritic flame-retardant layered silicate is applicable to rubber industry and cable industry, which can not only replace the traditional environmental-unfriendly flame-retardant and reinforcing material of high price, but also improve the performance of rubber material, such as flame resistance, mechanical properties and the like.
Description
Technical field
The present invention relates to a kind of dendritic flame-retardant layered silicate and preparation method thereof.
Background technology
The disaster that fire brings to the mankind is heavy, and loss is huge.Along with the development of economy and urban construction, fire losses is in rising trend, and therefore prevention of fires is very paid attention to both at home and abroad.In fire, have 1st/3rd among the dead personnel, because the toxic gas that discharges when sucking burning and death by suffocation.Halogenated flame retardant commonly used decomposites a large amount of toxic smogs in burning, easily make personnel on the scene poison, suffocate and influence vision and escape, and according to report in one's early years, halogen flame also has carcinogenic effect, and therefore a lot of developed countries ban use of.That oxyhydroxide integrates is fire-retardant, press down cigarette, fill triple functions, and nontoxic during burning, non-corrosiveness material produces, and raw material is easy to get, inexpensive, but because its add-on is bigger, serious to the mechanics and the electrical property influence of polymkeric substance.Therefore, research and development meet fire safety evaluating and environmental requirement, significant to the little BACN of the mechanics of material and electric property influence.
Polynite is be most widely used in the layered silicate a kind of.As layered silicate, polynite must make its intercalation or peel off in application process, could show the fire-retardant and reinforcing property of its uniqueness.1996, U.S. material scholar PaulCalvert is the last dispatch of top periodical " Nature " (Paul Calvert.Rough guide to thenanoworld.Nature in the world, 1996,383 (26): 300-301.) point out: the layered silicate after available process is peeled off is applied to and improves its hardness and rigidity in the polymkeric substance.(Hu Yuan such as Hu Yuan in addition, Song Lei. the flame-retardant polymer nano composite material. Chemical Industry Press, 2008.) point out: the synergistic key of nano composite polymer-montmorillonoid material and fire retardant is that organo montmorillonite has formed nanostructure in polymeric matrix, this structure promotes the surface of polynite that chemical reaction takes place conversely again, and then induce the generation of some physical actions, reduce the combustionproperty of polymkeric substance.
Dendritic polymer is a nova that was born in recent years and obtained developing rapidly, rise rapidly in material science.Because its highly branched structure and unique monodispersity make this compounds have special nature and function.Compare with linear macromolecule, the synthetic employing multistep multiple method of dendritic polymer, in the process that progressively increases, the relative molecular mass in each step is accurately controllable, and can select different branch subalgebras according to different purposes; Dendritic polymer has the geometrical symmetry of height, makes it become the ideal model of function sub-micron ball; Dendritic polymer has inner porous three-dimensional structure, and the end group that surface enrichment is a large amount of makes macromole have preferable reactive behavior; Dendritic polymer inside has a large amount of cavitys, helps the carrying out of Journal of Molecular Catalysis reaction; Owing to have accurate molecular structure, dendritic polymer is difficult to crystallization, also do not have chain and twine, thereby solvability, consistency improves greatly; In addition, because highly branched topological form makes the dendriform molecule have proximate globosity in three-dimensional space, its size between a few nanometer to tens nanometers, is typical nano material generally.
Polynite at present also exists many problems to wait further research and solves, as: the layered silicate flame retardant effect is not remarkable, the preparation of exfoliated organic montmorillonoid, and the solution of these problems is very crucial as the application of fire retardant for organo montmorillonite.Dendritic polymer is because its particular structure makes it that to a certain degree application be arranged in this field.
Summary of the invention
The purpose of this invention is to provide a kind of dendritic flame-retardant layered silicate and preparation method thereof, to overcome the defective of current material.
The present invention uses dendritic polymer, can introduce phosphorus, nitrogen ignition-proof element and zinc borate catalysis carbon-forming structure, to improve the flame retardant effect of organo montmorillonite, also can solve the peel off problem of stratiform polynite in solid polymeric material.
The preparation method of dendritic flame-retardant layered silicate of the present invention comprises the steps:
(1) preparation of high heat-resisting organo montmorillonite:
Inorganic polynite is mixed with the high heat-resisting intercalator that organises, add aqueous ethanolic solution, 75～80 ℃, stir 2～4h, solid-liquid separation is washed then, in 70～90 ℃ of vacuum-dryings, collects high heat-resisting organo montmorillonite;
The heat-resisting intercalator that organises of described height is the imidazole salts that contains phenyl ring, preferred 1-butyl-3-Methylimidazole hexafluorophosphate, phosphofluoric acid dialkylimidazolium salt or chlorination 1-(2-hydroxyethyl)-3-methylimidazole salt etc.;
The add-on of the high heat-resisting intercalator that organises is 50～70% of an aqueous ethanolic solution volume;
The alcoholic acid volumetric concentration is 40～60%, and in the aqueous ethanolic solution, the concentration of inorganic polynite is 0.5～1.5 g/mL;
Said inorganic polynite can be adopted business-like product, the product of the SMP trade mark of producing as Zhejiang Feng Hong clay company limited.
(2) the dendritic flame-retardant modification of high heat-resisting organo montmorillonite:
High heat-resisting organo montmorillonite with step (1), butanediamine, vinyl cyanide and mixture of catalysts, under nitrogen protection, stir 5～8 h in 70～90 ℃, vacuumize then to remove unreacted monomer, obtain containing grafted organo montmorillonite and the not dope of polymers grafted, from product, collect the dendriform organo montmorillonite then, concrete operations are as follows: the product methanol wash, centrifugation, throw out is again with centrifugal again behind the solvent wash, repeat above-mentioned steps till in washings, detecting, throw out in 30～50 ℃ of vacuum-drying 6～8 h, is obtained the dendriform organo montmorillonite less than unreacted matters and polymkeric substance;
Said catalyzer is a metal, preferred iron, cobalt or nickel etc.;
Described solvent is methyl alcohol, ethanol or Virahol etc.;
The weight percentage of high heat-resisting organo montmorillonite is 20～40% of a whole system;
Butanediamine: vinyl cyanide=1: 2～3, preferred 1: 2, mol ratio;
Butanediamine: catalyzer=1: 0.2～0.4, preferred 1: 0.3, mol ratio.
(3) the target fire retardant is synthetic:
With the dendriform organo montmorillonite of step (2) and α-(hexichol see base) acetate, under nitrogen protection, stir 1～2 h in 60～80 ℃, add the metal complexes zinc borate then and stir 2～4 h in 70～90 ℃, dendritic flame-retardant layered silicate;
The weight percentage of dendriform organo montmorillonite is 30～50% of a whole system;
α-(hexichol see base) acetate: zinc borate=1: 2～4, preferred 1: 3, mol ratio.
The prepared exfoliated nano level organo montmorillonite of dendroid of the present invention is applied in rubber industry and the cable industry, it is higher that both alternative or part substitutes traditional price, fire-retardant and the supporting material of unfriendly and infringement polymkeric substance other performance of environment, as: halogen flame, expansion type flame retardant, the oxyhydroxide fire retardant, white carbon black and carbon black etc., help the lifting of conventional industries, also can improve the performances such as fire-retardant and mechanics of elastomeric material, help opening the application market of Mineral resources such as polynite, so this achievement in research has considerable economic and certain social influence.
Embodiment
Adopt transmission electron microscope method to observe the size of particles of the exfoliated nano level organo montmorillonite of dendroid;
Adopt the thermogravimetry of " nano composite polymer/laminated silicate material theory and practice " (QiZongNeng, Shang Wenyu writes, Chemical Industry Press, 2002) regulation, the thermal weight loss core temperature of the dendritic exfoliated nano level organo montmorillonite of testing tree.
Embodiment 1
Take by weighing inorganic polynite of 75g and 25mL1-butyl-3-Methylimidazole hexafluorophosphate and join in the there-necked flask, and to add 50 mL volumetric concentrations be 40% aqueous ethanolic solution, be heated to about 75 ℃, stir 4 h, solid-liquid separation is washed then, in 70 ℃ of vacuum-dryings, get organo montmorillonite.
Take by weighing 40g organo montmorillonite, 1 mole of butanediamine, 2 mol propylene nitriles and 0.2 moles iron in four neck flasks; under nitrogen protection, stir 8 h in 70 ℃; vacuumize then to remove unreacted monomer, obtain containing grafted organo montmorillonite and the not dope of polymers grafted.The product methanol wash, centrifugation, throw out repeats above-mentioned steps till detecting less than unreacted matters and polymkeric substance again with centrifugal again after the methanol wash in washings.Throw out in 30 ℃ of vacuum-drying 8 h, is obtained the dendriform organo montmorillonite.
Take by weighing the dendriform organo montmorillonite of 150g and 1 mole of α-(hexichol see base) acetate in four neck flasks, under nitrogen protection,, add 2 mole metal title complex zinc borates then and stir 2 h in 90 ℃ in 60 ℃ of violent stirring 2 h, the target fire retardant.The size of particles of target fire retardant and thermal weight loss core temperature see Table 1.
Embodiment 2
Take by weighing the inorganic polynite of 60g and 36mL phosphofluoric acid dialkylimidazolium salt joins in the there-necked flask, and to add the 60mL volumetric concentration be 50% aqueous ethanolic solution, be heated to about 78 ℃, stir 3h, solid-liquid separation is washed then, in 80 ℃ of vacuum-dryings, get organo montmorillonite.
Take by weighing 50g organo montmorillonite, 1 mole of butanediamine, 2.5 mol propylene nitriles and 0.3 mole of cobalt in four neck flasks; under nitrogen protection, stir 6 h in 80 ℃; vacuumize then to remove unreacted monomer, obtain containing grafted organo montmorillonite and the not dope of polymers grafted.The product methanol wash, centrifugation, throw out repeats above-mentioned steps till detecting less than unreacted matters and polymkeric substance again with centrifugal again after the washing with alcohol in washings.Throw out in 40 ℃ of vacuum-drying 7 h, is obtained the dendriform organo montmorillonite.
Take by weighing the dendriform organo montmorillonite of 200g and 1 mole of α-(hexichol see base) acetate in four neck flasks, under nitrogen protection, stir 1.5h in 70 ℃, add 3 mole metal title complex zinc borates then and stir 3h in 80 ℃, the target fire retardant.The size of particles of target fire retardant and thermal weight loss core temperature see Table 1.
Embodiment 3
Take by weighing the inorganic polynite of 35g and 49mL chlorination 1-(2-hydroxyethyl)-3-methylimidazole salt joins in the there-necked flask, and to add 70 mL volumetric concentrations be 60% aqueous ethanolic solution, be heated to about 80 ℃, stir 2 h, solid-liquid separation is washed then, in 90 ℃ of vacuum-dryings, get organo montmorillonite.
Take by weighing 60g organo montmorillonite, 1 mole of butanediamine, 3 mol propylene nitriles and 0.4 moles iron in four neck flasks; under nitrogen protection, stir 5 h in 90 ℃; vacuumize then to remove unreacted monomer, obtain containing grafted organo montmorillonite and the not dope of polymers grafted.The product methanol wash, centrifugation, throw out repeats above-mentioned steps till detecting less than unreacted matters and polymkeric substance again with centrifugal again after the washed with isopropyl alcohol in washings.Throw out in 50 ℃ of vacuum-drying 6 h, is obtained the dendriform organo montmorillonite.
Take by weighing the dendriform organo montmorillonite of 250g and 1 mole of α-(hexichol see base) acetate in four neck flasks, under nitrogen protection, stir 1h in 80 ℃, add 4 mole metal title complex zinc borates then and stir 4h in 70 ℃, the target fire retardant.The size of particles of target fire retardant and thermal weight loss core temperature see Table 1.
The size of particles of table 1 target fire retardant and thermal weight loss core temperature
| Embodiment | Median size (nm) | The thermal weight loss core temperature (℃) |
| 1 | 20～30 | 250～300 |
| 2 | 30～40 | 300～350 |
| 3 | 40～50 | 350～400 |
Claims (4)
1. the preparation method of dendritic flame-retardant layered silicate is characterized in that, comprises the steps:
(1) get inorganic polynite and mix, add aqueous ethanolic solution with the high heat-resisting intercalator that organises, 75～80 ℃, stir 2～4h, collect high heat-resisting organo montmorillonite then;
(2) with high heat-resisting organo montmorillonite, butanediamine, vinyl cyanide and the mixture of catalysts of step (1),, from product, collect the dendriform organo montmorillonite then in 70～90 ℃ of stirring 5～8h;
Described catalyzer is iron, cobalt or nickel; The weight percentage of high heat-resisting organo montmorillonite is 20～40% of a whole system;
Butanediamine: vinyl cyanide=1: 2～3, butanediamine: catalyzer=1: 0.2～0.4;
(3) with the dendriform organo montmorillonite of step (2) and α-(hexichol see base) acetate, stir 1～2h in 60～80 ℃, add zinc borate then and stir 2～4h in 70～90 ℃, dendritic flame-retardant layered silicate;
The weight percentage of dendriform organo montmorillonite is 30～50% of a whole system;
α-(hexichol see base) acetate: zinc borate=1: 2～4, mol ratio;
The heat-resisting intercalator that organises of described height is 1-butyl-3-Methylimidazole hexafluorophosphate, phosphofluoric acid dialkylimidazolium salt or chlorination 1-(2-hydroxyethyl)-3-methylimidazole salt.
2. method according to claim 1 is characterized in that, the add-on of the high heat-resisting intercalator that organises is 50～70% of an aqueous ethanolic solution volume.
3. method according to claim 2 is characterized in that, in the aqueous ethanolic solution, the alcoholic acid volumetric concentration is 40～60%, and in the aqueous ethanolic solution, the concentration of inorganic polynite is 0.5～1.5g/mL.
4. according to the dendritic flame-retardant layered silicate of each described method preparation of claim 1～3.
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| CN102674385B (en) * | 2012-04-28 | 2013-10-16 | 上海工程技术大学 | Polymer modified layered silicate flame retardant and preparation method thereof |
| CN103254517A (en) * | 2013-05-30 | 2013-08-21 | 上海工程技术大学 | Flame-retardant ethylene propylene diene monomer rubber and preparation method thereof |
| CN103275378B (en) * | 2013-06-17 | 2015-09-30 | 上海工程技术大学 | A kind of fire-retardant dielectric substrate material used for printed circuit and preparation method thereof |
| CN103435846B (en) * | 2013-07-09 | 2014-11-26 | 上海工程技术大学 | Preparation method for dendritic organic/inorganic hybrid fire retardant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1475407A2 (en) * | 2003-05-08 | 2004-11-10 | Clariant GmbH | Flame retardant nanocomposite combination for thermoplastic polymers |
| CN1711217A (en) * | 2002-11-08 | 2005-12-21 | 澳大利亚聚合物股份有限公司 | Process for the preparation of polyolefin nanocomposites |
| CN101508800A (en) * | 2009-03-10 | 2009-08-19 | 上海工程技术大学 | Rubber material containing branched stripping type organic montmorillonite and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1711217A (en) * | 2002-11-08 | 2005-12-21 | 澳大利亚聚合物股份有限公司 | Process for the preparation of polyolefin nanocomposites |
| EP1475407A2 (en) * | 2003-05-08 | 2004-11-10 | Clariant GmbH | Flame retardant nanocomposite combination for thermoplastic polymers |
| CN101508800A (en) * | 2009-03-10 | 2009-08-19 | 上海工程技术大学 | Rubber material containing branched stripping type organic montmorillonite and preparation thereof |
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