CN1375516A - Nano composite polymer-montmorillonoid material and its prepn. - Google Patents
Nano composite polymer-montmorillonoid material and its prepn. Download PDFInfo
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- CN1375516A CN1375516A CN 01109845 CN01109845A CN1375516A CN 1375516 A CN1375516 A CN 1375516A CN 01109845 CN01109845 CN 01109845 CN 01109845 A CN01109845 A CN 01109845A CN 1375516 A CN1375516 A CN 1375516A
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Abstract
The nano composite material is formed from polypropylene whose molecular weight is 10-40 ten thousands and montmorillonoid whose content is 1-30 wt%. The scaled montmorillonoid can be uniformly dispersed in the polypropylene base body, the mechanical properties of said obtained material, including Young modulus, tensile strength, heat-resistance, thermal deformation temp. and thermal degradation temp., can be greatly raised. Said invention also discloses its production method.
Description
The present invention relates to a kind of nano composite polymer-montmorillonoid material and method for making thereof.
(one dimension is less than 10 at least because of its nanoscale effect for polymer nanocomposites
2Nm) and the performance and the polymer properties of inorganics perfectly combined, obtain the matrix material of excellent combination property.
CN 1138593A, CN 1163288A, CN 1242392A disclose nylon, polyester, polystyrene and polynite respectively and have prepared nano composite material.This method is only applicable to strong polar monomer synthetic composite material, and to nonpolar or low-pole monomer, as ethene, propylene etc. can not adopt this method to prepare molecular composite material.GB 2008598A. and WO, 79/01029 employing molecule complex method prepares the molecular composite material of inorganic/organic complex system, these methods are only applicable to the preparation of ethene/composite material of inorganic matter, can not be used for the stereospecific polymerization of alpha-olefin, be the electronic effect that these class methods do not have magnesium halide carrier on the one hand, catalyst activity is low; Be the synergy that does not have electron donor and magnesium halide on the other hand, can not get the poly-alpha olefins of stereospecific polymerization.
The object of the present invention is to provide a kind of nano composite polymer-montmorillonoid material, after montmorillonite layer is peeled off, be dispersed in the polypropylene matrix, the mechanical property of material comprises Young's modulus, tensile strength; Thermotolerance comprises that heat-drawn wire, thermal degradation temperature all are improved largely.
The present invention also aims to provide a kind of method for making of nano composite polymer-montmorillonoid material, it is low to have overcome in the prior art Composite Preparation efficient, the dispersion of inorganic materials in polyolefine do not reach nano level, and in-situ polymerization can not prepare the shortcoming of stereotaxis poly-alpha olefins matrix material.
A kind of nano composite polymer-montmorillonoid material of the present invention is made up of polypropylene and polynite, and described polypropylene molecule amount is 10～400,000, and described polynite content is 1～30% (weight meter).
The used polynite of the present invention is a kind of nonmetal stratiform silicate minerals, and its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two.The lamella internal surface has negative charge in the polynite, interlayer cation Na
2+, Ca
2+, Mg
2+Deng being the interchangeability positively charged ion, after cationic exchange, can make polysiloxane macromonomer insert the people to interlayer.Polynite should have cationic exchange total volume (CEC) 50～200meq/100g, is preferably 70～110meq/100g.When exchange capacity CEC greater than 200meq/100g, higher interlayer Coulomb's force makes polynite be difficult for being dispersed in the polymeric matrix; When exchange capacity is lower than 50meq/100g, polynite can not interact with polysiloxane macromonomer effectively, thereby is not enough to guarantee the consistency of polynite and polymeric matrix, makes polynite be difficult for being dispersed in the polymeric matrix equally.
The used polynite of the present invention should be crushed to suitable particle diameter with preceding, with ball mill, vibration mill jet mill etc. polynite is ground into desirable particle size then.General particle diameter should be at 40～100 μ m, and described in addition polynite is handled through organise intercalation processing and dehydration and deoxidation.
Polynite content (weight meter) is 1～30%, and when consumption is lower than 1%, polynite is not enough to produce enough enhancements; When consumption surpasses 30%, polynite can not be in polypropylene homodisperse.In the present invention, the preferred content scope of polynite is 1～20%.Cationite of the present invention is a quaternary ammonium salt, comprise the quaternary ammonium salt that contains hexadecyl, octadecyl, allyl group, acrylamido, propylene ester group etc., as: cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, allyl group trimethyl ammonium chloride, acrylamido trimethyl ammonium chloride, propylene ester-trimethyl ammonium chloride etc.
The method for making of a kind of nano composite polymer-montmorillonoid material of the present invention in turn includes the following steps: (by weight)
A. the processing that organises of natural montmorillonite
With the cationic exchange total volume is that 50～200meq/100g, particle diameter are 0.5～40 part of the polynite of 40～100 μ m, and high-speed stirring in the presence of 80～1000 parts dispersion medium forms stable montmorillonite suspension liquid; 0.5～15 part of cationite is dissolved in 20～100 parts of dispersion medium, adds 0.01～1.0 part of protonating agent, form solution; This drips of solution is added on is heated in 70～90 ℃ of polynite aaerosol solutions, will make polynite colloidal sol, this colloidal sol suction filtration, washing are not had white precipitate for extremely to dripping silver nitrate solution through 0.5～2 hour; Then through vacuum-drying, with ball mill, vibration mill or jet mill pulverize the organic montmorillonoid of particle diameter 20～100 μ m;
B. the preparation of polynite magnesium chloride complex carrier
With the vacuum-drying 10～20 hours under 80～100 ℃ of conditions of the organic montmorillonoid of gained, under nitrogen protection with 100 parts of organo montmorillonites and 20～40 parts of anhydrous MgCl
2With 5～10 parts of electron donors, as organoalkoxysilane, ethyl benzoate, dibutyl phthalate, 2,2,6, the 6-tetramethyl piperidine gets polynite magnesium chloride complex carrier with ball mill or vibration mill grinding after 24～48 hours.Complex carrier is added 300～400 parts of distilled toluene be mixed into soup compound under nitrogen atmosphere.
C. the preparation of carried-type active polynite
Get 100 parts of soup compounies and under nitrogen atmosphere, drip 300～700 parts of TiCl
4Reacted 1～3 hour down in 80～110 ℃, wash 5～10 times, vacuum-drying promptly gets the carried-type active polynite.
D. the preparation of composite nanometer-level polypropylene/montmorillonoid material
Reactor repeatedly behind the pump drainage charged pressure be the propylene monomer of 50～75mmHg, with the solvent that 100 parts of drying treatment are crossed, can be toluene or hexane, 0.1～0.5 part of AlEt
3With 0.02～0.1 part of electron donor such as organoalkoxysilane, ethyl benzoate, dibutyl phthalate, 2,2,6, the 6-tetramethyl piperidine, injecting reactor adds behind 2～6 parts of activated montmorillonite clays 60～90 ℃ of reactions 0.5～10 hour down, product stops through acidifying ethanol, filter, drying promptly gets composite nanometer-level polypropylene/montmorillonoid material.
It should be noted: only as the basis of determining other raw material consumptions in this step, the umber value in the different step does not have comparative to the umber value in above each step.
The protonating agent that the present invention was suitable for can be sulfuric acid, hydrochloric acid, sulfonic acid, acetic acid, Tricholroacetic Acid, phosphoric acid, m-phthalic acid or phthalic acid etc.
The effect of the dispersion medium that the present invention is used is to promote the dispersion of montmorillonite particle and the carrying out of cation exchange reaction, can be water, ethanol, methyl alcohol, Virahol, N, dinethylformamide etc.
The nanometer composite polypropylene material of montmorillonoid-containing of the present invention is an exfoliated nano-composite, and dispersive montmorillonite-based nano lamella is dispersed in the polypropylene matrix.
The nanometer composite polypropylene material of montmorillonoid-containing of the present invention makes polynite have very big interfacial area, inorganic disperse phase and polypropylene-base body interface have the ideal adhesiveproperties, can eliminate inorganics and polymeric matrix two material thermal expansivity mismatch problems.
The nanometer composite polypropylene material of montmorillonoid-containing of the present invention because the nanoscale effect of nano imvite lamella has strengthened inorganics and polymeric matrix interphase interaction, is greatly improved the mechanical property of matrix material.
The iris action of the nano imvite of sheet can make heat-resisting, the flame retardant resistance of material be greatly improved in the nanometer composite polypropylene material of montmorillonoid-containing of the present invention.The adding of sheet nano imvite has also improved the solvent resistance of matrix material simultaneously.
Simple, the easy row of the preparation manipulation of the nanometer composite polypropylene material of montmorillonoid-containing of the present invention utilizes the production unit of plain polypropylene can prepare composite nanometer-level polypropylene/montmorillonoid material.Omitted the melt blending step among traditional polypropylene/inorganic filler preparation method, product can be directly used in injection moulding.
The present invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
With the cationic exchange total volume is the polynite 5g that 90meq/100g, particle diameter are about 40 μ m, and high-speed stirring in the presence of the dispersion medium water of 100ml forms stable montmorillonite suspension liquid; 3.2g cationite octadecyl trimethyl ammonium chloride is dissolved in the 30ml dispersion medium water, adds 0.05g protonating agent hydrochloric acid, form solution; This drips of solution is added on is heated in 80 ℃ of polynite aaerosol solutions,, make polynite colloidal sol, this colloidal sol suction filtration, repetitive scrubbing are not had white precipitate for extremely to dripping silver nitrate solution through 2 hours; Then through vacuum-drying, rub with ball mill, vibration mill or injection and to pulverize to such an extent that particle diameter is about the organic montmorillonoid of 40 μ m.
With the vacuum-drying 20 hours under 90 ℃ of conditions of the organic montmorillonoid of gained, under nitrogen protection with 15g organo montmorillonite and the anhydrous MgCl of 5g
2Get polynite magnesium chloride complex carrier with 2ml electron donor dibutyl phthalate after 36 hours with ball mill, vibration mill grinding.
Complex carrier is added the distilled toluene of 50ml be mixed into soup compound under nitrogen atmosphere.Get 10g soup compound Dropwise 5 0ml TiCl under nitrogen atmosphere
4Reacted 2 hours down in 85 ℃, promptly get the carried-type active polynite with 7 vacuum-drying of dry normal heptane washing.
The solvent toluene that reactor charges into the propylene monomer of 770mmHg pressure repeatedly behind the pump drainage, the 500ml drying treatment is crossed, 1g AlEt
3With 0.2g dimethoxy phenylbenzene silicon injecting reactor successively, reacted 1 hour down at 80 ℃ after the polynite of adding 2g carried-type active, product stops through acidifying ethanol, filters, and drying promptly gets composite nanometer-level polypropylene/montmorillonoid material.Its performance sees Table 1.
Embodiment 2
The preparation of carried-type active polynite is with embodiment 1.
Solvent hexane, 1g AlEt that reactor charges into the propylene monomer of 770mmHg pressure repeatedly behind the pump drainage, the 500ml drying treatment is crossed
3With 0.3g methyl butyl dimethoxy silane, injecting reactor reacted 2.5 hours down at 80 ℃ behind the adding 2g active earths successively, and product stops through acidifying ethanol, filters, and drying promptly gets composite nanometer-level polypropylene/montmorillonoid material.Its performance sees Table 1.
Embodiment 3
The preparation of carried-type active polynite is with embodiment 1.
Solvent hexane, 1g AlEt that reactor charges into the propylene monomer of 770mmHg pressure repeatedly behind the pump drainage, the 500ml drying treatment is crossed
3With 0.3g 2,2,6, the 6-tetramethyl piperidine, injecting reactor reacted 2.5 hours down at 80 ℃ behind the adding 2g active earths successively, and product stops through acidifying ethanol, filters, and drying promptly gets composite nanometer-level polypropylene/montmorillonoid material.Its performance sees Table 1.
Comparative Examples
The anhydrous MgCl of 5g
2Get magnesium chloride support after 30 hours with the grinding of 2ml electron donor dimethoxy diphenyl silane vibration mill.
Magnesium chloride support is added the distilled toluene of 50ml be mixed into soup compound under nitrogen atmosphere.Get 10g soup compound Dropwise 5 0ml TiCl under nitrogen atmosphere
4Reacted 2 hours down in 90 ℃, promptly get loaded catalyst with 7 vacuum-drying of dry normal heptane washing.
Reactor charges into the propylene monomer of 770mmHg pressure behind the pump drainage repeatedly, with the solvent that the 500ml drying treatment is crossed, can be toluene or hexane, 1g AlEt
3With 0.2g electron donor such as dimethoxy phenylbenzene silicon injecting reactor successively, add behind the 0.5g loaded catalyst 80 ℃ of reactions 1 hour down, product stops through acidifying ethanol, filters, and drying promptly gets polypropylene material.Its performance sees Table 1.
Table 1
| Embodiment | Reaction times (hour) | Polynite content (wt%) | Young's modulus (GPa) | Tensile strength (MPa) | Extension at break (%) | Heat-drawn wire (℃) | Thermal degradation temperature *(℃) |
| ??1 | ??1 | ??2.5 | ??2.08 | ??43.5 | ??325 | ??138 | ??460 |
| ??2 | ??2.5 | ??4.6 | ??2.22 | ??55.5 | ??375 | ??144 | ??440 |
| ??3 | ??5 | ??8.1 | ??2.43 | ??48.3 | ??250 | ??151 | ??- |
| Comparative Examples | ??1 | ??0 | ??1.42 | ??41.6 | ??400 | ??110 | ??416 |
Temperature when * thermal degradation temperature is material thermal weight loss speed maximum herein.
Claims (6)
1. a nano composite polymer-montmorillonoid material is made up of polypropylene and polynite, and described polypropylene molecule amount is 10～400,000, and described polynite content is 1～30% (weight meter);
Described polynite has cationic exchange total volume (CEC) 50～200meq/100g;
Described polynite particle diameter is 40～100 μ m, and handles through organise intercalation processing and dehydration and deoxidation.
2. according to a kind of nano composite polymer-montmorillonoid material of claim 1, it is characterized in that described polynite has cationic exchange total volume (CEC) 70～110meq/100g.
3. according to a kind of nano composite polymer-montmorillonoid material of claim 1, it is characterized in that described polynite content is 1～20% (weight meter).
4. the method for making of a nano composite polymer-montmorillonoid material, (by weight) in turn includes the following steps:
A. the processing that organises of natural montmorillonite
With the cationic exchange total volume is that 50～200meq/100g, particle diameter are 0.5～40 part of the polynite of 40～100 μ m, and high-speed stirring in the presence of 80～1000 parts dispersion medium forms stable montmorillonite suspension liquid; 0.5～15 part of cationite is dissolved in 20～100 parts of dispersion medium, adds 0.01～1.0 part of protonating agent, form solution; This drips of solution is added on is heated in 70～90 ℃ of polynite aaerosol solutions, will make polynite colloidal sol, this colloidal sol suction filtration, washing are not had white precipitate for extremely to dripping silver nitrate solution through 0.5～2 hour; Then through vacuum-drying, with ball mill, vibration mill or injection rub pulverize the organic montmorillonoid of particle diameter 20～100 μ m;
B. the preparation of polynite magnesium chloride complex carrier
With the vacuum-drying 10～20 hours under 80～100 ℃ of conditions of the organic montmorillonoid of gained, under nitrogen protection with 100 parts of organo montmorillonites and 20～40 parts of anhydrous MgCl
2With 5～10 parts of electron donors, get polynite magnesium chloride complex carrier after 24～48 hours with ball mill or vibration mill grinding; Complex carrier is added 300～400 parts of distilled toluene be mixed into soup compound under nitrogen atmosphere;
C. the preparation of carried-type active polynite
Get 100 parts of soup compounies and under nitrogen atmosphere, drip 300～700 parts of TiCl
4Reacted 1～3 hour down in 80～110 ℃, wash 5～10 times, vacuum-drying promptly gets the carried-type active polynite;
D. the preparation of composite nanometer-level polypropylene/montmorillonoid material
Reactor repeatedly behind the pump drainage charged pressure be the propylene monomer of 50～75mmHg, toluene or hexane solvent that 100 parts of drying treatment are crossed, 0.1～0.5 part of AlEt
3With 0.02～0.1 part of electron donor injecting reactor, add behind 2～6 parts of activated montmorillonite clays 60～90 ℃ of reactions 0.5～10 hour down, product stops through acidifying ethanol, filters drying;
Described electron donor is organoalkoxysilane, ethyl benzoate, dibutyl phthalate, 2,2,6, the 6-tetramethyl piperidine;
Described cationite is a quaternary ammonium salt;
Described protonating agent is sulfuric acid, hydrochloric acid, sulfonic acid, acetic acid, Tricholroacetic Acid, phosphoric acid, m-phthalic acid or phthalic acid;
Described dispersion medium is water, ethanol, methyl alcohol, Virahol, N, dinethylformamide.
5. according to the method for making of a kind of nano composite polymer-montmorillonoid material of claim 4, it is characterized in that described cationite is the quaternary ammonium salt that contains hexadecyl, octadecyl, allyl group, acrylamido, propylene ester group.
6. according to the method for making of a kind of nano composite polymer-montmorillonoid material of claim 4, it is characterized in that described cationite is cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride, allyl group trimethyl ammonium chloride, acrylamido trimethyl ammonium chloride, propylene ester-trimethyl ammonium chloride.
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| CN102532708B (en) * | 2011-12-28 | 2013-12-18 | 株洲时代工程塑料制品有限责任公司 | Modified polypropylene composition |
| CN104785226A (en) * | 2015-04-15 | 2015-07-22 | 陕西科技大学 | Glass powder enhanced Zr modification montmorillonite honeycomb block chromium sorbent and preparation method thereof |
| CN104785226B (en) * | 2015-04-15 | 2017-04-26 | 陕西科技大学 | Glass powder enhanced Zr modification montmorillonite honeycomb block chromium sorbent and preparation method thereof |
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| CN107602920A (en) * | 2017-09-26 | 2018-01-19 | 福州大学 | A kind of preparation method of montmorillonite load type polypropylene beta crystal nucleating agent |
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