CN101638492A - Layered double hydroxide and preparation method of montmorillonite nanometer composite material - Google Patents
Layered double hydroxide and preparation method of montmorillonite nanometer composite material Download PDFInfo
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Abstract
The invention discloses a layered double hydroxide and a preparation method of a montmorillonite nanometer composite material, aiming at obtaining an organic modified layered double hydroxide and an organic modified montmorillonoid prepared by using an organic modification method and obtaining the layered double hydroxide and montmorillonite-halogen-free flame retardant rubber nanometer compositematerial prepared by using a smelting blending method through complex, wherein a conventional flame retardant agent can be added in the composite material. The nanometer composite material has favorable physical and chemical properties, heat stability, flame retardant property and mechanical property and can be used as heat stabilizers, flame retardant agents, biology/medical materials, ultraviolet/infrared absorption materials, electrochemistry/electronics materials, and the like.
Description
Technical field:
The invention belongs to rubber-inorganic nano composite material technical field, relate in particular to the preparation method of the collaborative halogen-free fireproof rubber nano composite material of a kind of layered double-hydroxide and polynite.
Background technology:
Nanosecond science and technology are the forward position intercrossing emerging fields that grow up late 1980s, nano composite material is meant the solid phase by two or more, the material that its phase size is composited with nanoscale size at one dimension at least, it is the important component part of nano material engineering; Wherein, the polymer/inorganic laminated nano composition is blended together rigidity, dimensional stability and the thermostability of inorganics and toughness, workability and the dielectric properties of polymkeric substance, thereby produce many new specific performances, layered double-hydroxide and polynite are the mineral compound with laminate structure; Wherein, layered double-hydroxide is meant that ideal consists of [M
2+ mM
3+ n(OH)
2m+2n]
N+A
P- N/pMH
2The class of O has the mineral compound of laminate structure, M
2+Be divalent-metal ion, comprise: Mg
2+, Zn
2+, Fe
2+, Cu
2+, Ca
2+, Sn
2+, Cr
2+, Pb
2+M
3+Be trivalent metal ion, comprise: Al
3+, Cr
3+, Mn
3+, Fe
3+, Ti
3+, Ga
3+A is an interlayer anion, comprising: NO
3 -, OH
-, Cl
-, Br
-, I
-, CO
3 2-, SO
4 2-, SO
3 2-, CrO
4 2-, PO
4 3-, V
10O
28 6-, monocarboxylic acid root such as p-nitrobenzoic acid root, aryl phosphoric acids roots such as phosphenylic acid root; M and n make m/n=1～6, and 2～4 value preferably is more preferably near 3 value; The integer of p=1～10; M is generally 2～6 integer in 0～10 scope; Often be known as di-hydroxyl composite metal oxidate and layer dihydroxy complex hydroxide in the literature.Polynite mainly with the form existence of montmorillonite (popular name wilkinite), is the hydrous alumino silicates mineral in the Nature, belong to montmorillonite family.It is 2: 1 type layered silicates, and each unit cell constitutes by carrying 1 layer of alumina octahedral secretly in the middle of 2 silicon-oxy tetrahedrons, has negative charge between its layer mineral, can absorb Ca
2+, Mg
2+, K
+, Na
+Deng positively charged ion, and has cation exchange property.The crystal chemistry of montmorillonite and crystalline structure have determined polynite to have many operational characteristiies, as cationic exchange, swelling property, dispersiveness and wetting ability, agglutinating value(of coal) and plasticity-, stability, thixotropy, suspension etc.Layered double-hydroxide and polynite have important use as additive in macromolecular material, can be used as thermo-stabilizer, fire retardant, biology/medical material, ultraviolet/infrared absorbing material, electrochemistry/electronics material etc.
" nano composite material that comprises rubber and modified layered double hydroxide; Its Preparation Method And Use " that number of patent application 200680045192b proposes, " a kind of polyvinyl chloride/laminate double-hydroxide nanocomposite and preparation method thereof " that number of patent application 200810114897 proposes is with layered double-hydroxide and the polymer/laminated double-hydroxide nanocomposite of the compound preparation of polymkeric substance.
" a kind of method for preparing organophilic bentonite using fusion intercalation method " that number of patent application 200510097027.8 proposes is a kind of method for preparing organophilic bentonite using fusion intercalation method, belongs to the bentonite preparing technical field." a kind of halogen-free flame-proof highly anti-flush polyphenylacetylene composition and preparation method thereof " that number of patent application 200710099609.9 proposes, be that each component is mixed the back melt blending and made polyphenylacetylene combination by described amount, wherein adopted poly-2,6-dimethyl-1, the mixture of 4-phenyl ether and nano kaoline." a kind of flame-proof epoxide resin nano compound material " that number of patent application 200710043762 proposes is organo montmorillonite to be joined prepare Resins, epoxy/organic montmorillonite nano composite material in the Resins, epoxy.
Summary of the invention:
The preparation method who the purpose of this invention is to provide the collaborative halogen-free fireproof rubber nano composite material of a kind of layered double-hydroxide and polynite, adopt organic modifiers to prepare organically-modified layered double-hydroxide and organic modification montmonrillonite, synergy by organically-modified layered double-hydroxide and organic modification montmonrillonite, prepare the halogen-free fireproof rubber nano composite material, and prepare the halogen-free fireproof rubber nano composite material by the method for melt blending.
The present invention is achieved through the following technical solutions:
The preparation method of a kind of layered double-hydroxide and Nano composite material of montmorillonite, be to adopt organically-modified method, prepare organically-modified layered double-hydroxide and organic modification montmonrillonite, by composite, and adopt melt-mixing method to prepare layered double-hydroxide and the collaborative halogen-free fireproof rubber nano composite material of polynite, its concrete preparation method comprises following processing step:
A. organically-modified layered double-hydroxide is synthetic
In the mixed aqueous solution that contains divalent-metal ion and trivalent metal ion, divalent-metal ion and trivalent metal ion mol ratio are 1～5, the metal ion total concn is in the mixed aqueous solution of 0.1～5 mol, add anion-modified dose of 0.5～1.5 times of trivalent metal ion integral molar quantity, under 10～90 ℃, dripping weight concentration and be 5～50% alkaline solution to pH value is 7～12, after the reaction 5～72 throw out is filtered, washing and drying, obtains organically-modified layered double-hydroxide;
B. organic modification montmonrillonite is synthetic
With cation exchange capacity is polynite 0.5-40 part of 50-120mol/100g, and high-speed stirring in the presence of 100-1000 part dispersion medium water forms stable dispersion system A;
8-12 part trimeric cyanamide is added in 100-1000 part dispersion medium water, add 8-12 part protonating agent phosphoric acid, under 60-90 ℃, after high-speed stirring 3-6 hour, cold filtration is used washed with de-ionized water, and oven dry prepares cation modifier melamine phosphate salt; 0.1-30 part cation modifier melamine phosphate salt is added in 100-1000 part dispersion medium water, form dispersion system B;
Dispersion system A is heated to 60-90 ℃, dispersion system B slowly is added dropwise among the dispersion system A, after high-speed stirring 3-6 hour, cold filtration is used washed with de-ionized water, and oven dry is pulverized and obtained organic modification montmonrillonite;
C. the halogen-free fireproof rubber nano composite material is worked in coordination with in layered double-hydroxide and polynite
With organically-modified layered double-hydroxide 1-10 part, organic modification montmonrillonite 1-10 part, 100 parts of melt blendings in Banbury mixer of untreated rubber, processing temperature 80-100 ℃, rotor speed 34-136rpm, total mixing time 10-20min, at untreated rubber, organically-modified layered double-hydroxide, behind the organic modification montmonrillonite mixing 3-10min, add vulcanization leveller, vulcanizing agent, vulcanization accelerator adds conventional flame retardants 30-90 part, until mixing end, with this mixture discharging sulfuration, promptly get product.
The preparation method of described layered double-hydroxide and Nano composite material of montmorillonite is characterized in that: the divalent-metal ion in the described mixed aqueous solution is Mg
2+, Zn
2+, Fe
2+, Cu
2+, Ca
2+, Sn
2+, Cr
2+, pb
2+In a kind of, trivalent metal ion is Al
3+, Cr
3+, Mn
3+, Fe
3+, Ti
3+, Ga
3+In a kind of.
The preparation method of described layered double-hydroxide and Nano composite material of montmorillonite is characterized in that: described alkaline solution is the aqueous solution or the ammoniacal liquor of sodium hydroxide, potassium hydroxide, calcium hydroxide.
The preparation method of described layered double-hydroxide and Nano composite material of montmorillonite is characterized in that: described anion-modified dose comprises a kind of in p-nitrobenzoic acid or the disodium phenylphosphate or their mixture.
The preparation method of described layered double-hydroxide and Nano composite material of montmorillonite is characterized in that: described untreated rubber is terpolymer EP rubber, natural rubber, paracril, a kind of in the styrene-butadiene rubber(SBR).
The preparation method of described layered double-hydroxide and Nano composite material of montmorillonite, it is characterized in that: described vulcanization leveller, vulcanizing agent, vulcanization accelerator select for use respectively zinc oxide, sulphur ,] thiazole accelerator, conventional flame retardants is selected magnesium hydroxide, aluminium hydroxide, microcapsule red phosphorus, zinc sulphide, melamine and derivative thereof, phosphorus compound and/or boron compound for use.
Advantage of the present invention is:
Nano composite material of the present invention has good physical and chemical performance, thermostability, flame retardant properties and mechanical property.
Embodiment:
Embodiment 1:
The 100g terpolymer EP rubber, the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil joins in the Banbury mixer.90 ℃ of melting temperatures, spinner velocity 40rpm, mixing time 10min.With this mixture discharging sulfuration, the cross-linked rubber test piece that promptly gets Comparative Examples.Its performance sees Table 1.
Embodiment 2:
0.3mol MgCl
26H
2The AlCl of O and 0.1mol
36H
2O is dissolved in the 300mL deionized water, adds the 0.1mol p-nitrobenzoic acid, stirs evenly, and is designated as solution A.The NaOH solution of preparation 0.1mol/L is some, be designated as solution B. under 60 ℃ of constant temperatures, slowly be added dropwise among the A B and vigorous stirring, regulate pH to 8.0～9.0, the reaction 72h after with throw out filtration, washing, drying, obtain the organically-modified layered double-hydroxide of p-nitrobenzoic acid, called after LDH-pNBA.
With 100g terpolymer EP rubber and 10g LDH-pNBA, join in the Banbury mixer 90 ℃ of melting temperatures, spinner velocity 40rpm, total mixing time 15min.Behind LDH-pNBA and the mixing 8min of terpolymer EP rubber, add the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil, the 90g magnesium hydroxide continues mixing.Then with this mixture discharging sulfuration.Its performance sees Table 1.
Embodiment 3:
With cation exchange capacity is the polynite 20g of 90mmol/100g, and high-speed stirring in the presence of 500ml dispersion medium water forms stable dispersion system A.The 10g trimeric cyanamide is added in the dispersion medium water, add 10g protonating agent phosphoric acid, under 60-90 ℃, after high-speed stirring 3-6 hour, cold filtration is used washed with de-ionized water, and oven dry prepares cation modifier melamine phosphate salt.4g cation modifier melamine phosphate salt is added in the 500ml dispersion medium water, form dispersion system B.Dispersion system A is heated to 60-90 ℃, dispersion system B slowly is added dropwise among the dispersion system A, after high-speed stirring 3-6 hour, cold filtration is used washed with de-ionized water, and oven dry is ground into organic modification montmonrillonite MPM.
With 100g terpolymer EP rubber and 8g LDH-pNBA, 2g MPM joins in the Banbury mixer, 90 ℃ of melting temperatures, spinner velocity 40rpm, total mixing time 15min.Behind LDH-pNBA, MPM and the mixing 8min of terpolymer EP rubber, add the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil, the 90g magnesium hydroxide continues mixing.Then with this mixture discharging sulfuration.Its performance sees Table 1.
Embodiment 4:
With 100g terpolymer EP rubber and 5g LDH-pNBA, 5g MPM joins in the Banbury mixer, 90 ℃ of melting temperatures, spinner velocity 40rpm, total mixing time 15min.Behind LDH-pNBA, MPM and the mixing 8min of terpolymer EP rubber, add the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil, the 90g magnesium hydroxide continues mixing.Then with this mixture discharging sulfuration.Its performance sees Table 1.
Embodiment 5:
With 100g terpolymer EP rubber and 2g LDH-pNBA, 8g MPM joins in the Banbury mixer, 90 ℃ of melting temperatures, spinner velocity 40rpm, total mixing time 15min.Behind LDH-pNBA, MPM and the mixing 8min of terpolymer EP rubber, add the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil, the 90g magnesium hydroxide continues mixing.Then with this mixture discharging sulfuration.Its performance sees Table 1.
Embodiment 6:
100g terpolymer EP rubber and 10g MPM are joined in the Banbury mixer 90 ℃ of melting temperatures, spinner velocity 40rpm, total mixing time 15min.Behind LDH-pNBA, MPM and the mixing 8min of terpolymer EP rubber, add the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil, the 90g magnesium hydroxide continues mixing.Then with this mixture discharging sulfuration.Its performance sees Table 1.
Embodiment 7:
0.3mol MgCl
26H
2The AlCl of O and 0.1mol
36H
2O is dissolved in the 300mL deionized water, adds the 0.05mol disodium phenylphosphate, stirs evenly, and is designated as solution A.The NaOH solution of preparation 0.1mol/L is some, be designated as solution B. under 60 ℃ of constant temperatures, slowly be added dropwise among the A B and vigorous stirring, regulate pH to 8.0～9.0, the reaction 72h after with throw out filtration, washing, drying, obtain the organically-modified layered double-hydroxide of disodium phenylphosphate, called after LDH-PPP.
With 100g terpolymer EP rubber and 10g LDH-PPP, join in the Banbury mixer 90 ℃ of melting temperatures, spinner velocity 40rpm, total mixing time 15min.Behind LDH-PPP and the mixing 8min of terpolymer EP rubber, add the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil, the 90g magnesium hydroxide continues mixing.Then with this mixture discharging sulfuration.Its performance sees Table 1.
Embodiment 8:
With 100g terpolymer EP rubber and 8g LDH-PPP, 2g MPM joins in the Banbury mixer, 90 ℃ of melting temperatures, spinner velocity 40rpm, total mixing time 15min.Behind LDH-PPP, MPM and the mixing 8min of terpolymer EP rubber, add the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil, the 90g magnesium hydroxide continues mixing.Then with this mixture discharging sulfuration.Its performance sees Table 1.
Embodiment 9:
With 100g terpolymer EP rubber and 5g LDH-PPP, 5g MPM joins in the Banbury mixer, 90 ℃ of melting temperatures, spinner velocity 40rpm, total mixing time 15min.Behind LDH-PPP, MPM and the mixing 8min of terpolymer EP rubber, add the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil, the 90g magnesium hydroxide continues mixing.Then with this mixture discharging sulfuration.Its performance sees Table 1.
Embodiment 10:
With 100g terpolymer EP rubber and 2g LDH-PPP, 8g MPM joins in the Banbury mixer, 90 ℃ of melting temperatures, spinner velocity 40rpm, total mixing time 15min.Behind LDH-PPP, MPM and the mixing 8min of terpolymer EP rubber, add the 20g carbon black, 2g sulphur, the 2g thiazole accelerator, 5g zinc oxide, the 2g amines antioxidants, the 5g plasticizing oil, the 90g magnesium hydroxide continues mixing.Then with this mixture discharging sulfuration.Its performance sees Table 1.
Claims (6)
1, the preparation method of a kind of layered double-hydroxide and Nano composite material of montmorillonite, be to adopt organically-modified method, prepare organically-modified layered double-hydroxide and organic modification montmonrillonite, by composite, and adopt melt-mixing method to prepare layered double-hydroxide and the collaborative halogen-free fireproof rubber nano composite material of polynite, its concrete preparation method comprises following processing step:
A. organically-modified layered double-hydroxide is synthetic
In the mixed aqueous solution that contains divalent-metal ion and trivalent metal ion, divalent-metal ion and trivalent metal ion mol ratio are 1～5, the metal ion total concn is in the mixed aqueous solution of 0.1～5 mol, add anion-modified dose of 0.5～1.5 times of trivalent metal ion integral molar quantity, under 10～90 ℃, dripping weight concentration and be 5～50% alkaline solution to pH value is 7～12, after the reaction 5～72 throw out is filtered, washing and drying, obtains organically-modified layered double-hydroxide;
B. organic modification montmonrillonite is synthetic
With cation exchange capacity is polynite 0.5-40 part of 50-120mol/100g, and high-speed stirring in the presence of 100-1000 part dispersion medium water forms stable dispersion system A;
8-12 part trimeric cyanamide is added in 100-1000 part dispersion medium water, add 8-12 part protonating agent phosphoric acid, under 60-90 ℃, after high-speed stirring 3-6 hour, cold filtration is used washed with de-ionized water, and oven dry prepares cation modifier melamine phosphate salt; 0.1-30 part cation modifier melamine phosphate salt is added in 100-1000 part dispersion medium water, form dispersion system B;
Dispersion system A is heated to 60-90 ℃, dispersion system B slowly is added dropwise among the dispersion system A, after high-speed stirring 3-6 hour, cold filtration is used washed with de-ionized water, and oven dry is pulverized and obtained organic modification montmonrillonite;
C. the halogen-free fireproof rubber nano composite material is worked in coordination with in layered double-hydroxide and polynite
With organically-modified layered double-hydroxide 1-10 part, organic modification montmonrillonite 1-10 part, 100 parts of melt blendings in Banbury mixer of untreated rubber, processing temperature 80-100 ℃, rotor speed 34-136rpm, total mixing time 10-20min, at untreated rubber, organically-modified layered double-hydroxide, behind the organic modification montmonrillonite mixing 3-10min, add vulcanization leveller, vulcanizing agent, vulcanization accelerator adds conventional flame retardants 30-90 part, until mixing end, with this mixture discharging sulfuration, promptly get product.
2, the preparation method of layered double-hydroxide according to claim 1 and Nano composite material of montmorillonite is characterized in that: the divalent-metal ion in the described mixed aqueous solution is Mg
2+, Zn
2+, Fe
2+, Cu
2+, Ca
2+, Sn
2+, Cr
2+, Pb
2+In a kind of, trivalent metal ion is Al
3+, Cr
3+, Mn
3+, Fe
3+, Ti
3+, Ga
3+In a kind of.
3, the preparation method of layered double-hydroxide according to claim 1 and Nano composite material of montmorillonite is characterized in that: described alkaline solution is the aqueous solution or the ammoniacal liquor of sodium hydroxide, potassium hydroxide, calcium hydroxide.
4, the preparation method of layered double-hydroxide according to claim 1 and Nano composite material of montmorillonite is characterized in that: described anion-modified dose comprises a kind of in p-nitrobenzoic acid or the disodium phenylphosphate or their mixture.
5, the preparation method of layered double-hydroxide as claimed in claim 1 and Nano composite material of montmorillonite is characterized in that: described untreated rubber is terpolymer EP rubber, natural rubber, paracril, a kind of in the styrene-butadiene rubber(SBR).
6, the preparation method of layered double-hydroxide as claimed in claim 1 and Nano composite material of montmorillonite, it is characterized in that: described vulcanization leveller, vulcanizing agent, vulcanization accelerator select for use respectively zinc oxide, sulphur ,] thiazole accelerator, conventional flame retardants is selected magnesium hydroxide, aluminium hydroxide, microcapsule red phosphorus, zinc sulphide, melamine and derivative thereof, phosphorus compound and/or boron compound for use.
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| CN101638492B (en) | 2011-07-20 |
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