CN100390229C - Polyolefine/alkyl phosphate modified montmorillonite nano compound material, its manufacturing method and uses - Google Patents
Polyolefine/alkyl phosphate modified montmorillonite nano compound material, its manufacturing method and uses Download PDFInfo
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- CN100390229C CN100390229C CNB2004100989250A CN200410098925A CN100390229C CN 100390229 C CN100390229 C CN 100390229C CN B2004100989250 A CNB2004100989250 A CN B2004100989250A CN 200410098925 A CN200410098925 A CN 200410098925A CN 100390229 C CN100390229 C CN 100390229C
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Abstract
The present invention particularly relates to a polyolefin / alkyl phosphorus modification montmorillonite nanocomposite material with heat processing stability and a preparing method and a use for the material, which belongs to the field of polyolefin/ montmorillonite nanocomposite materials. The composite material of the present invention comprises components of the following proportion by weight: 0.01-10 shares of montmorillonite, 87 to 100 shares of polyolefin basal bodies and 0.005 to 3 shares of alkyl diphenylbenzene halogenated phosphor modifiers; sheet layers of the montmorillonite are striped and dispersed in the polyolefin basal bodies. The alkyl diphenylbenzene halogenated phosphor modifiers have good heat stability so as to cause the composite material to have good heat processing stability. After the nanocomposite material of the present invention is in heat processing, the nanocomposite material still keeps a good discontinuous phase dimension and distribution. Simultaneously, the synthesized productivity of the alkyl diphenylbenzene halogenated phosphor modifiers is high.
Description
Technical field
The invention belongs to the polyolefin/montmorillonite nano composite material field, particularly have polyolefine/alkyl phosphate modified montmorillonite nano compound material and the method for making and the purposes of hot-work stability.
Background technology
Stripping polyolefin/Nano composite material of montmorillonite is a kind of nano composite material of ideal structure, this structure is evenly distributed in the polyolefin substrate with nano-scale owing to polynite, small-size effect, surface and interfacial effect and quantum effect by the montmorillonite-based nano lamella, under considerably less filler, (generally be less than 5wt%) and improve the mechanical property and the thermal characteristics of polyolefine material, and the gasproof body barrier of polyolefin articles and flame retardant properties etc., thereby widen the Application Areas of polyolefine material, realize the high performance of general purpose material.Exfoliated nano composite material is a kind of nano composite material of ideal structure, because polynite is dispersed in the polyolefin substrate with the nanometer sheet form, thereby its physical and mechanical property and some other performance significantly improve than body material.
The polymer melt intercalation is compound and solution intercalation is compound (J Mater Sci, 1996,31:4307; JMater Sci Lett, 1997,16:1670; J Appl Polym Sci, 1997,66:1781; Macromolecules, 1997,30:6333; Polym Bull, 1998,41:107; J Eng MaterTechnol, 1999,121:483; Polymer, 2001,42:9633; Macromol Rapid Commun, 2001,22:176; 1 J Mater Sci, 2000,35:1045; Though) can be used to prepare composite polyolefine material, can only obtain the exfoliated matrix material of intercal type or part usually, be difficult to obtain exfoliated polyolefin/montmorillonite nano composite material fully.The use of a large amount of organic solvents is totally unfavorable to material aftertreatment and environment protection in the solution intercalation recombination process.
In-situ monomer intercalation polymerization (Chem Commun, 1999:2179; Macromol RapidCommun, 1999,20:423; DE 19846314 (2000); Macromol Rapid Commun, 2000,21:57; Macromol Rapid Commun 2002,23:135-140) in-situ polymerization by olefinic monomer prepares intercal type and exfoliated nano composite material.The in-situ inserted polymerization of report adopts metallocene catalyst mostly at present, because metallocene catalyst costs an arm and a leg, promotor methylaluminoxane (MAO) consumption is big simultaneously, makes preparation cost improve; And metallocene catalyst synthesis of polyolefins degree of isotacticity and melt temperature are lower, thereby limit its industrialization.The Institute of Chemistry, Academia Sinica at inventor place adopts the ziegler-Natta/MMT composite catalyst, successfully prepare the composite nanometer-level polypropylene/montmorillonoid material of high upright structure degree of isotacticity by in-situ polymerization, and polyethylene/montmorillonite nanometer composite material (CN02119744.X, CN 02157888.5, and CN 02157887.7).Discovering subsequently, although can prepare exfoliated nano-composite by situ aggregation method, but olefin polymerization nanometer composite material is after process hot-work (extruding or injection moulding), exfoliated structure is owing to the thermolysis of organic ammonium is damaged, montmorillonite layer self aggregation (Macromol Rapid Commun 2002,23:135～140) again after hot-work.The inventor adopts imidazoles properties-correcting agent to the polynite processing that organises, and it is compound with the Z-N catalyzer, the polymerization of catalyzing propone in-situ monomer intercalation, successfully prepare exfoliated nano-composite, the Nano composite material of montmorillonite of the more common alkylamine modification of this material is compared, and has better thermal stability (CN200410009491.2).But imidazoles properties-correcting agent synthetic yield is undesirable, and the alkyl microcosmic salt that the present invention adopts not only has good thermostability, also has very high yield simultaneously, thereby is more suitable for being used to prepare olefin polymerization nanometer composite material.
Summary of the invention
One of purpose of the present invention is at high temperature unstable at present organic ammonium properties-correcting agent, its elevated temperature heat degraded causes the self aggregation again of polynite in the matrix material, thereby change the nanophase structure of matrix material, a kind of polyolefine/alkyl microcosmic salt Nano composite material of montmorillonite modified with hot-work stability is provided.
Two of purpose of the present invention provides the synthetic method of heat resistant type alkyl microcosmic salt.
Three of purpose of the present invention provides the preparation method of the polyolefine/alkyl microcosmic salt Nano composite material of montmorillonite modified with hot-work stability.Adopt heat resistant type alkyl microcosmic salt modification Na-MMT, and prepare TiCl by chemical reaction method
4/ MgCl
2/ organo montmorillonite (MMT) composite catalyst, composite catalyst catalyzed alkene monomer in-situ polymerization, thus prepare the stable polyolefin/montmorillonite nano composite material of hot-work.
Four of purpose of the present invention is to overcome by in-situ polymerization that montmorillonite layer is difficult to peel off in the existing Physical Processing technology, and the original position between montmorillonite layer generates and prepares the stripping polyolefin/alkyl microcosmic salt Nano composite material of montmorillonite modified with hot-work stability by polymerization reaction heat and polymkeric substance.
Five of purpose of the present invention is to utilize cheap Z-N catalyzer, and catalyzing propone is prepared high stereotaxis, dystectic poly-alpha olefins; Introduce the thermostability of alkyl microcosmic salt properties-correcting agent, thereby prepare polyolefine/alkyl phosphate modified montmorillonite nano compound material with hot-work stability with the raising matrix material.
Six of purpose of the present invention provides the purposes of the polyolefine/alkyl microcosmic salt Nano composite material of montmorillonite modified with hot-work stability.
Contain polynite 0.01～10 weight part in polyolefine/alkyl microcosmic salt Nano composite material of montmorillonite modified with hot-work stability of the present invention, polyolefin substrate 87～100 weight parts, alkyl microcosmic salt properties-correcting agent 0.005～3 weight part, montmorillonite layer is peeled off and is dispersed in the polyolefin substrate.
Alkyl microcosmic salt class properties-correcting agent used in the nano composite material of the present invention has not only improved the consistency of polarity polynite and non-polar polyolefinic, and has given matrix material better hot-work stability.Nano composite material of the present invention is still keeping dispersed phase size and distribution preferably through after the hot-work.
Specific surface area 50～the 1000m of described polynite
2/ g, aperture 5～50nm, pore volume 0.3～500cm
3/ g, cation exchange capacity is preferably 100～120meq/100g.Described polynite is Na-polynite, K-polynite, Ca-polynite or Li-polynite.
Described polyolefine is polyethylene, polypropylene or polyethylene and polypropylene alloy.
Described alkyl phosphate modified dose is alkyl triphenyl halo phosphorus, and wherein the structure of alkyl is CH
3-(CH
2) n-(9≤n≤10000); Halogen is Br, I or Cl.
The polyolefine/preparation method of alkyl microcosmic salt Nano composite material of montmorillonite modified with hot-work stability of the present invention follows these steps to carry out:
(1) alkyl triphenyl halo phosphorus properties-correcting agent is synthetic
Triphenyl phosphorus is joined in the reactor, intensification makes its dissolving, add haloalkane then, the mol ratio of haloalkane and triphenyl phosphorus is 1～1.3: 1, in 70～130 ℃ of reactions 12～200 hours, add after petroleum ether filters, add hexane wash again and filter, place vacuum drying oven in 40～50 ℃ of dryings 24 hours.
The structure of alkyl is CH in the described haloalkane
3-(CH
2) n-(9≤n≤10000).Haloalkane such as dodecyl chloro alkane, tetradecyl alkyl chloride, hexadecyl chloro alkane, octadecyl chloro alkane, nonadecyl alkyl chloride, eicosyl alkyl chloride, dodecyl bromo alkane, tetradecyl bromoalkane, hexadecyl bromoalkane, octadecyl bromo alkane, nonadecyl bromoalkane, eicosyl bromoalkane, dodecyl idoalkane, tetradecyl idoalkane, hexadecyl idoalkane, octadecyl iodo alkane, nonadecyl idoalkane or eicosyl idoalkane etc.
(2) processing that organises of polynite
With 1 weight part Na-polynite, the K-polynite, Ca-polynite or Li-polynite were stirred 1～100 hour in 10～100 weight part distilled water in 30～90 ℃, add the alkyl triphenyl halo phosphorus that step (1) obtains and the mixing solutions of acidic alcohol then, wherein acidic alcohol mixing solutions concentration is 1～80wt%, the mol ratio of hydrochloric acid and alkyl triphenyl iodate phosphorus is 0.1～1.3: 1, the weight part ratio of alkyl triphenyl halo phosphorus and polynite is 0.4～5 in the mixing solutions of adding polynite: 1, above-mentioned mixing solutions in 30～90 ℃ stir 1～24 hour after suction filtration, with washing with alcohol until no free halogen ion, place 30～100 ℃ of vacuum-dryings after 10～24 hours then, grind to form about 40～60 microns powder of particle diameter, then in 80 ℃ of vacuum-dryings after 8 hours the airtight preservation of atmosphere of inert gases standby.
(3) TiCl
4/ MgCl
2The preparation of/MMT composite catalyst
Solid magnesium halogenide is dissolved in the decane solution of alcohol, obtaining concentration is the magnesium halogenide decane solution of 5～80wt%, and wherein alcohol is 1～4: 1 with magnesium halogenide mol ratio, adds acid anhydrides then, acid anhydrides and pure mol ratio 0～1: 1 obtain transparent magnesium halide solution; Add the treated organo montmorillonite of step (2), wherein polynite is 1～20: 1 with solid magnesium halide weight ratio, after 60～140 ℃ of constant temperature stir 2～24 hours, standing over night, supernatant liquid is siphoned away, then mixture is added drop-wise in-20～0 ℃ the titanium compound, the weight ratio of titanium compound and polynite is 10～50: 1, and-20～0 ℃ was stirred 0.5～2 hour, and was warming up to 80～130 ℃, add ester compound, the weight ratio of ester compound and polynite is 0～1: 1, stirs 2～20 hours at 80～130 ℃ of constant temperature, behind the heat filtering, add titanium compound again, the weight ratio of titanium compound and polynite is 10～50: 1, in 80～130 ℃ of reactions 2～20 hours, filters, with anhydrous hexane or heptane heat washing 2～6 times, the weight percentage that drying obtains titanium is at the composite catalyst of 0.5～6% montmorillonoid-containing.
(4). have the polyolefine/alkyl phosphate modified montmorillonite nano compound material of hot-work stability
Under ethene or propylene monomer atmosphere, with anhydrous hexane, heptane or toluene organic solvent join in the reactor, add the n-heptane solution that concentration is the aluminum compound of 1.0～5.0mol/L then successively, (composite catalyst of titaniferous polynite can be used anhydrous hexane earlier to the composite catalyst of the titaniferous polynite of organosilicon and step (3) preparation, heptane or toluene organic solvent were carried out pre-treatment 0.5～20 hour, 0.01 the polynite of～500 weight parts can be with the organic solvent of 0.5～80000 weight part), wherein the Al/Ti mol ratio 10～300: 1, Si/Al mol ratio 0～1: 1, ethene or propylene monomer pressure 1～40 normal atmosphere, 30～90 ℃ of polymerization temperatures, after 0.5～5 hour reaction times, acidifying ethanol (adding 1～10000 weight part acidifying ethanol) termination reaction that adds 1～10wt% as polynite with respect to 0.01～500 weight part, heat agitated 20～60 minutes, washing is dry, the polyolefine/alkyl phosphate modified montmorillonite nano compound material that obtains having hot-work stability.The major ingredient of nano composite material is the polynite of 0.01～10 weight part, the polyolefin substrate of 87～100 weight parts, 0.005 the alkyl triphenyl iodate phosphorus properties-correcting agent of～3 weight parts, the montmorillonite layer in the nano composite material is peeled off and is dispersed in the polyolefin substrate.
Described magnesium halogenide is MgCl
2, MgBr
2Or MgI
2, wherein preferred MgCl
2
Described titanium compound is a tetravalent titanium halide, and tetravalent titanium halide is TiCl
4, TiBr
4Or TiI
4, wherein preferred TiCl
4
Described alcohol is butanols, sec-n-octyl alcohol, 1-octanol or isooctyl alcohol.
Described acid anhydrides is Tetra hydro Phthalic anhydride, trimellitic anhydride or Pyroglutaric acid.
Described ester compound is ethyl acetate, propyl propionate, butyl butyrate, dibutyl phthalate or dipropyl phthalate.
Described organosilicon molecular formula is as follows: R
nSi (OR ')
4-nWherein to represent carbonatoms be C for R or R '
1～C
8Alkane or aromatic hydrocarbon, 0≤n≤3 are as phenylbenzene dimethoxy silicon, phenylbenzene diethoxy silicon or phenylbenzene dibutoxy silicon.
Described aluminum compound is aluminum alkyls or aikyl aluminum halide.
Described aluminum alkyls: as triethyl aluminum or triisobutyl aluminium; Aikyl aluminum halide: as dimethyl monochlor(in)ate aluminium, monomethyl al dichloride, diethyl monochlor(in)ate aluminium, an ethylaluminum dichloride, diisobutyl monochlor(in)ate aluminium or an isobutyl-al dichloride.Wherein preferred triethyl aluminum.
Described rare gas element is high pure nitrogen or argon gas.
In preparation method of the present invention, when acid anhydrides, ester compound and silicon compound content were 0, it was active high to be used to prepare polyethylene; When acid anhydrides, ester compound and silicon compound content were not 0, active height and stereospecificity were good when being used to prepare polypropylene.
Polyolefine/alkyl phosphate modified montmorillonite nano compound material of the present invention can be used for the starting material in fields such as automobile component, food packaging industry, motion goods, electrical equipment.The low filling, the more traditional packing material of high performance olefin polymerization nanometer composite material has clear superiority.Polyolefin/laminated nano composite material particular performances will be brought more wide application prospect to this class material with combining of lower production cost, thereby also widen the Application Areas and the scope of polyolefine material.
Preparation method with polyolefine/alkyl microcosmic salt Nano composite material of montmorillonite modified of hot-work stability of the present invention has following characteristics:
1. preparation method of the present invention adopts the method for in-situ polymerization to prepare stripping polyolefin/alkyl microcosmic salt Nano composite material of montmorillonite modified, and wherein montmorillonite layer is dispersed in the polyolefin substrate with nano-grade size.
2. the present invention adopts heat resistant type alkyl microcosmic salt properties-correcting agent to handle polynite, makes the polyolefine/alkyl microcosmic salt Nano composite material of montmorillonite modified of preparation have good hot-work stability, thereby has guaranteed the uniform distribution of composite product nano-dispersed phase.
3. the invention provides the novel method of preparation high yield alkyl microcosmic salt properties-correcting agent.
4. the synthetic method of adopting montmorillonite supported catalysts and present industrial some polyolefine Preparation of catalysts resemble process that adopts among the preparation method of the present invention, help suitability for industrialized production, and when being used for propylene polymerization, tacticity can reach more than 95%, and fusing point is up to 160 degree.
5. polyolefine/alkyl microcosmic salt Nano composite material of montmorillonite modified the wide accommodation with hot-work stability of the present invention, the molecular weight of polymkeric substance is controlled, can adopt slurry polymerization, mass polymerization or gaseous polymerization to prepare polyolefine/alkyl microcosmic salt Nano composite material of montmorillonite modified.
Shown in accompanying drawing 1 and 4, it is the XRD figure of the composite powder sample of the embodiment of the invention 1,3 and embodiment 14,2 θ show that at 1.5～10 ° of characteristic diffraction peaks of not finding polynite (001) face the matrix material of in-situ polymerization preparation is an exfoliated nano-composite; Shown in Fig. 2 and 3, be the embodiment of the invention 1 and embodiment 3 matrix material on the Minimax-183 injection moulding machine in 200 ℃ shear 2 minutes respectively after the injection moulding batten, the batten of injection moulding is tested through XRD, 2 θ are at 1.5～10 ° of characteristic diffraction peaks of not finding polynite (001) face, show that matrix material montmorillonite layer after Overheating Treatment does not take place significantly to assemble, TEM result is consistent with the XRD structure.With number of patent application CN 02119744.X, CN02157888.5, the Nano composite material of montmorillonite of the polyolefine among the CN 02157887.7/alkylammonium modification is compared, polyolefine/the alkyl phosphate modified montmorillonite nano compound material of the present invention's preparation has better hot-work stability, thereby guarantees the stability of composite material nanometer phase structure.
Description of drawings
Fig. 1. the XRD figure of the embodiment of the invention 1 and 3 composite powder samples.
Fig. 2. the XRD figure of sample after the embodiment of the invention 1 and 200 ℃ of injection mouldings of 3 matrix materials.
The TEM of sample figure after 200 ℃ of injection mouldings of Fig. 3 embodiment of the invention 1 matrix material.
The XRD figure of Fig. 4 embodiment of the invention 14 composite powder samples.
Embodiment
Specific surface area 50～the 1000m of the polynite among the embodiment
2/ g, aperture 5～50nm, pore volume 0.3～500cm
3/ g, cation exchange capacity 100～120meq/100g.
The preparation of hexadecyl triphenyl iodate phosphorus: triphenyl phosphorus 7.1 grams, join in the 250ml reaction flask, be warming up to 80 ℃ and make its fusion, drip the iodohexadecane of 10ml, 80 ℃ of stirring reactions are after 14 hours, the reaction system very thickness that becomes, add 100ml petroleum ether and stirring washing after-filtration, add 100ml hexane agitator treating again and filter, obtain pressed powder in 40 ℃ of vacuum-dryings 24 hours, obtain the 16.5g product, yield is 91%.
The preparation of microcosmic salt-ethanolic soln: take by weighing the hexadecyl triphenyl iodate phosphorus of 8g, add the dilute hydrochloric acid solution of 60ml ethanol and 1.2ml 36wt%, standby after 1 hour in 50 ℃ of stirrings.
The preparation of organo montmorillonite: with 6.33 gram sodium-polynites in 200ml distilled water 60 ℃ stirred 20 hours, add above-mentioned microcosmic salt-ethanolic soln then, violent stirring is suction filtration after 4 hours, with the hot ethanol washing until AgNO
3Check does not have precipitation.Place 80 ℃ of vacuum-dryings after 10 hours then, grind powder into about 40～60 microns, then in 80 ℃ of vacuum-dryings after 8 hours the rare gas element argon atmospher to enclose airtight preservation standby.
Preparation of catalysts: the 3.31g Magnesium Chloride Anhydrous is scattered in the 20mL n-decane in 130 ℃, add the 14mL isooctyl alcohol, constant temperature stirred after 2 hours, add the 0.58g Tetra hydro Phthalic anhydride, continue to keep 130 ℃ of constant temperature to stir after 1 hour, be cooled to 60 ℃, add the above-mentioned organo montmorillonite 6.76g that handles well, keep 60 ℃ of constant temperature to stir standing over night after 6 hours, take supernatant liquid away, be added drop-wise to 200ml-20 ℃ TiCl then
4Solution stirred 0.5 hour in-20 ℃ of maintenance constant temperature, slowly was warming up to 110 ℃, added the 2.6mL dibutyl phthalate, stirred 6 hours at 110 ℃ of constant temperature, behind the heat filtering, added the TiCl of 120mL
4, filter after 4 hours in 110 ℃ of reactions, with the hot washing and filtering of anhydrous hexane, each 80mL washs 5 times altogether.Obtain TiCl after the drying
4/ MgCl
2The weight percentage that/MMT catalyzer, spectrophotometer record titanium in the catalyzer is 1.3.
The preparation of nanometer composite polypropylene material: under the atmosphere of propylene monomer, the 200mL normal heptane is added in the reactor, the n-heptane solution (1.8mol/L) that adds the 3.78mL triethyl aluminum successively, 1.34mL the n-heptane solution (0.5mmol/mL) of dimethoxy phenylbenzene silicon and the catalyzer 0.25g of montmorillonite load, propylene monomer pressure 0.5Mpa, 60 ℃ of polymerization temperatures, after 2 hours reaction times, add 10wt% acidifying ethanol 50ml termination reaction, heat agitated 30 minutes, washing is dry, obtain 24.2g polynite nanometer composite polypropylene material, polynite accounts for 0.8 weight part in matrix material, the weight part of hexadecyl triphenyl phosphorus in matrix material is 0.24, and polyolefin substrate accounts for 99 weight parts.
The characteristic of operational condition and composite nanometer-level polypropylene/montmorillonoid material is listed in table 1.
(001) face has the last one diffraction peak at 2 θ=3.2 degree on the hexadecyl triphenyl phosphorus montmorillonite modified X-ray powder diffraction spectrogram, X-ray powder diffraction 2 θ of sample 1 do not have diffraction peak at the 1.5-10 degree, according to Bragg equation 2dsin θ=λ, the interlamellar spacing that can calculate organo montmorillonite is greater than 5.8nm.Test result shows that this nano composite material is an exfoliated nano-composite.This material can be used for preparing automotive industry component, wrapping material, motion goods, electrical component.
The preparation of nonadecyl triphenyl phosphorus chloride: triphenyl phosphorus 6 grams, join in the 250ml reaction flask, be warming up to 120 ℃ and make its fusion, drip the chloro nonadecane of 7.73g, 120 ℃ of stirring reactions added 100ml petroleum ether and stirring washing after-filtration after 150 hours, adding 100ml hexane agitator treating again filters, obtain pressed powder in 40 ℃ of vacuum-dryings 24 hours, obtain the 12.6g product, yield is 92%.
The preparation of microcosmic salt-ethanolic soln: take by weighing the nonadecyl triphenyl phosphorus chloride of 6.26g, add the dilute hydrochloric acid solution of 40ml ethanol and 2ml 8wt%, standby after 1 hour in 50 ℃ of stirrings.
The preparation of organo montmorillonite: with 6 gram sodium-polynites in 200ml distilled water 60 ℃ stirred 20 hours, add above-mentioned microcosmic salt-ethanolic soln then, violent stirring is suction filtration after 8 hours, with the hot ethanol washing until AgNO
3Check does not have precipitation.Place 80 ℃ of vacuum-dryings after 10 hours then, grind powder into about 40～60 microns, then in 80 ℃ of vacuum-dryings after 8 hours the rare gas element argon atmospher to enclose airtight preservation standby.
Preparation of catalysts and raw material: with embodiment 1.
The preparation of composite nanometer-level polypropylene/montmorillonoid material: the catalyzer 0.25g of montmorillonite load added 5ml heptane stir process 1.5 hours.Under the atmosphere of propylene monomer, the 200mL normal heptane is added in the reactor, the n-heptane solution (1.8mol/L) that adds the 3.78mL triethyl aluminum successively, 1.34mL the n-heptane solution (0.5mmol/mL) of dimethoxy phenylbenzene silicon, add preprocessed catalyst solution then, propylene monomer pressure 0.5Mpa, 60 ℃ of polymerization temperatures, after 2 hours reaction times, add 10wt% acidifying ethanol 50ml termination reaction, heat agitated 30 minutes, washing is dry, obtain 60.7g polynite nanometer composite polypropylene material, polynite accounts for 0.15 weight part in matrix material, the weight part of hexadecyl triphenyl phosphorus in matrix material is 0.05, and polyolefin substrate accounts for 99.8 weight parts.
Other technology is with embodiment 1, and the characteristic of operational condition and composite nanometer-level polypropylene/montmorillonoid material is listed in the table 1.
The preparation and the raw material of hexadecyl triphenyl iodate phosphorus: with embodiment 1.
Organic cations preparation and raw material: with embodiment 1.
The preparation of organo montmorillonite and raw material: with embodiment 1.
Preparation of catalysts and raw material: with embodiment 1.
The preparation of composite nanometer-level polypropylene/montmorillonoid material: other is with embodiment 1, and the characteristic of operational condition and composite nanometer-level polypropylene/montmorillonoid material is listed in the table 1.
Table 1 embodiment 1～8
| Embodiment | Catalyst pretreatment time hour | The Al/Ti mol ratio | The Al/Si mol ratio | Temperature, ℃ | Alkene pressure Mpa | Time hour | Catalytic efficiency Kg.molTi -1 | Polynite wt% | Fusing point T m ℃ | Degree of isotacticity % | Heat decomposition temperature T onset ℃ |
| 1 | 0 | 100 | 10 | 60 | 0.5 | 2 | 355 | 0.8 | 161 | 98.2 | 359 |
| 2 | 1.5 | 100 | 10 | 60 | 0.5 | 2 | 1953 | 0.15 | 163 | 95.5 | 341 |
| 3 | 24 | 100 | 10 | 60 | 0.5 | 2 | 402 | 0.7 | 163 | 98 | 371 |
| 4 | 11 | 100 | 10 | 70 | 0.3 | 1 | 606 | 0.4 | 163 | 94 | 352 |
| 5 | 11 | 100 | 10 | 40 | 0.3 | 1 | 546 | 0.5 | 161 | 92 | 358 |
| 6 | 11 | 100 | 10 | 60 | 0.3 | 1 | 873 | 0.3 | 163 | 97.5 | 342 |
| 7 | 1 | 100 | 10 | 70 | 0.3 | 0.5 | 1299.6 | 0.2 | 164 | 99 | 342 |
| 8 | 1 | 100 | 10 | 40 | 0.3 | 0.5 | 825.6 | 0.33 | 163 | 96 | 344 |
The data of table 1 show, the polyacrylic melt temperature that adopts this Preparation of Catalyst is up to 164 ℃, the insolubles content that boiling n-heptane records is up to 99%, show that synthetic polypropylene is high isotaxy type polypropylene, the gained nanometer composite polypropylene material is exfoliated nanometer composite polypropylene material (see figure 1), and heat decomposition temperature obviously improves than the common organic amine Nano composite material of montmorillonite modified of PP/ of in-situ polymerization preparation.Nano material is carried out the XRD test once more after 200 ℃ of injection mouldings, do not find significantly (001) diffraction peak, and MMT is dispersed in the PP matrix, shows that this material has the hot-work stability of improvement (seeing Fig. 2,3).This material can be used for preparing automotive industry component, wrapping material, motion goods, electrical component.
The preparation of hexadecyl tri-phenyl-phosphorus bromide: triphenyl phosphorus 5 grams, join in the 250ml reaction flask, be warming up to 120 ℃, drip the 7.5g bromohexadecane, 120 ℃ of stirring reactions are after 24 hours, the reaction system very thickness that becomes, add 100ml petroleum ether and stirring washing after-filtration, add 100ml hexane agitator treating again and filter, obtain pressed powder, obtain the 11.7g product in 40 ℃ of vacuum-dryings 24 hours.
The preparation of microcosmic salt-ethanolic soln: take by weighing the hexadecyl tri-phenyl-phosphorus bromide of 6.1g, add the diluted hydrochloric acid aqueous solution of 35ml ethanol and 5ml 8wt%, standby after 1 hour in 50 ℃ of stirrings.。
The preparation of organo montmorillonite: with 4 gram sodium-polynites in 250ml distilled water 60 ℃ stirred 24 hours, add above-mentioned microcosmic salt-ethanolic soln then, violent stirring is suction filtration after 12 hours, with the hot ethanol washing until AgNO
3Check does not have precipitation.Place 80 ℃ of vacuum-dryings after 10 hours then, grind powder into about 40～60 microns, then in 80 ℃ of vacuum-dryings after 8 hours the rare gas element argon atmospher to enclose airtight preservation standby.
Preparation of catalysts: the 1g Magnesium Chloride Anhydrous is scattered in the 20mL n-decane in 130 ℃, add the 4.1mL isooctyl alcohol, constant temperature stirred after 2 hours, be cooled to 60 ℃, add the above-mentioned organo montmorillonite 4g that handles well, keep 60 ℃ of constant temperature to stir standing over night after 6 hours, take supernatant liquid away, be added drop-wise to 200ml-20 ℃ TiCl then
4Solution stirred 1 hour in-20 ℃ of maintenance constant temperature, slowly was warming up to 110 ℃, stirred 2 hours at 110 ℃ of constant temperature, behind the heat filtering, added the TiCl of 120mL
4In 8 hours after-filtration of 110 ℃ of reactions, with the hot washing and filtering of anhydrous hexane, each 100mL washs 5 times altogether.Obtain TiCl after the drying
4/ MgCl
2The weight percentage that/MMT catalyzer, spectrophotometer record titanium in the catalyzer is 1.2.
The preparation of polyethylene nano composite material: under the atmosphere of vinyl monomer, the 200mL normal heptane is added in the reactor, add the n-heptane solution (1.8mol/L) of 0.24mL triethyl aluminum and the catalyzer 0.02g of montmorillonite load successively, propylene monomer pressure 0.3Mpa, 60 ℃ of polymerization temperatures, after 30 minutes reaction times, add 10wt% acidifying ethanol 50ml termination reaction, heat agitated 30 minutes, washing is dry, obtains 9.31g polynite nanometer composite polypropylene material, and polynite accounts for 0.15 weight part in matrix material, the weight part of hexadecyl triphenyl phosphorus in matrix material is 0.05, and polyolefin substrate accounts for 99.8 weight parts.
The characteristic of operational condition and composite nanometer-level polypropylene/montmorillonoid material is listed in table 2.
The preparation and the raw material of hexadecyl triphenyl iodate phosphorus: with embodiment 9.
Organic cations preparation and raw material: with embodiment 9.
The preparation of organo montmorillonite and raw material: with embodiment 9.
Preparation of catalysts and raw material: with embodiment 9.
The preparation of composite nanometer-level polypropylene/montmorillonoid material: other is with embodiment 9, and the characteristic of operational condition and composite nanometer-level polypropylene/montmorillonoid material is listed in the table 2.
Table 2 embodiment 9～14
| Embodiment | Solvent | Al/Ti mol/mol | Si，ml | Catalytic activity kgPEmol Ti -1 | MMT wt％ | T m ℃ | T c ℃ | Heat decomposition temperature T onset ℃ |
| 9 | Toluene | 80 | 0 | 1710 | 0.15 | 133.7 | 120.0 | 445 |
| 10 | Toluene | 100 | 0 | 2570 | 0.1 | 134.5 | 119.5 | 446 |
| 11 | Toluene | 120 | 0 | 2970 | 0.08 | 134.0 | 119.7 | 446 |
| 12 | Heptane | 60 | 0 | 960 | 0.26 | 134.2 | 120.3 | 445 |
| 13 | Heptane | 80 | 0 | 2530 | 0.1 | 134.3 | 119.7 | 446 |
| 14 | Heptane | 100 | 0 | 1270 | 0.2 | 134.2 | 130.7 | 445 |
The data of table 2 show that prepared PE matrix material cheating engaging layer spacing in XRD test shows matrix material has good thermal stability (seeing Table 2) greater than 6 nanometer (see figure 4)s.
The polyethylene/montmorillonite nanometer composite material of the present invention's preparation can be used for preparing automotive industry component, plastic film for agricultural use, wrapping material, motion goods, electrical component.
Claims (13)
1. polyolefine/alkyl phosphate modified montmorillonite nano compound material, it is characterized in that: contain polynite 0.01～10 weight part in described polyolefine/alkyl phosphate modified montmorillonite nano compound material, polyolefin substrate 87～100 weight parts, alkyl phosphate modified dose 0.005～3 weight part, montmorillonite layer is peeled off and is dispersed in the polyolefin substrate;
Described alkyl phosphate modified dose is alkyl triphenyl halo phosphorus; Wherein the structure of alkyl is CH
3-(CH
2) n-, 9≤n≤10000; Halogen is Cl, Br or I.
2. material according to claim 1 is characterized in that: described polynite is Na-polynite, K-polynite, Ca-polynite or Li-polynite; Specific surface area 50～the 1000m of described polynite
2/ g, aperture 5～50Bmm, pore volume 0.3～500cm
3/ g, cation exchange capacity are 100～120meq/100g.
3. material according to claim 1 is characterized in that: described polyolefine is polyethylene, polypropylene or polyethylene and polypropylene alloy.
4. one kind according to each described preparation methods of claim 1～3, and it is characterized in that: described preparation method follows these steps to carry out:
(1) alkyl triphenyl halo phosphorus properties-correcting agent is synthetic
Triphenyl phosphorus is joined in the reactor, heat up and make its dissolving, add haloalkane then, the mol ratio of haloalkane and triphenyl phosphorus is 1～1.3: 1, and in 70～130 ℃ of reactions 12～200 hours, washing and filtering placed the vacuum drying oven drying;
(2) processing that organises of polynite
Under 30～90 ℃ of temperature, in polynite, add distilled water, stir, add the alkyl triphenyl halo phosphorus that step (1) obtains and the mixing solutions of acidic alcohol then, wherein acidic alcohol mixing solutions concentration is 1～80wt%, the mol ratio of hydrochloric acid and alkyl triphenyl halo phosphorus is 0.1～1.3: 1, and the weight part ratio of alkyl triphenyl halo phosphorus and polynite is 0.4～5 in the mixing solutions of adding polynite: 1; Mix solution, suction filtration, washing is not to there being free halogen ion, and vacuum-drying grinds to form the powder of 40～60 microns of particle diameters, and the airtight preservation of atmosphere of inert gases is standby;
(3) preparation of composite catalyst
Solid magnesium halogenide is dissolved in the decane solution of alcohol, obtaining concentration is the magnesium halogenide decane solution of 5～80wt%, and wherein alcohol is 1～4: 1 with magnesium halogenide mol ratio, adds acid anhydrides then, acid anhydrides and pure mol ratio 0～1: 1 obtain transparent magnesium halide solution;
Add the treated organo montmorillonite of step (2), wherein polynite is 1～20: 1 with solid magnesium halide weight ratio, stir in 60～140 ℃ of constant temperature, leave standstill, supernatant liquid is siphoned away, then mixture is added drop-wise in-20～0 ℃ the titanium compound, stir, the weight ratio of titanium compound and polynite is 10～50: 1, is warming up to 80～130 ℃, add ester compound, stir, the weight ratio of ester compound and polynite is 0～1: 1, filters, add titanium compound again, the weight ratio of titanium compound and polynite is 10～50: 1, in 80～130 ℃ of reactions, filters, the weight percentage that washing, drying obtain titanium is at the composite catalyst of 0.5～6% montmorillonoid-containing;
Wherein ester compound is ethyl acetate, propyl propionate, butyl butyrate, dibutyl phthalate or dipropyl phthalate;
(4). have the polyolefine/alkyl phosphate modified montmorillonite nano compound material of hot-work stability
Under ethene or propylene monomer atmosphere, anhydrous hexane, heptane or toluene solvant are joined in the reactor, the composite catalyst of titaniferous polynite that adds n-heptane solution, organosilicon and step (3) preparation of aluminum alkyls or aikyl aluminum halide then successively, wherein the Al/Ti mol ratio 10～300: 1, Si/Al mol ratio 0～1: 1, ethene or propylene monomer pressure 1～40 normal atmosphere, 30～90 ℃ of polymerization temperatures; Add acidifying ethanol termination reaction, stir, washing is dry, the polyolefine/alkyl phosphate modified montmorillonite nano compound material that obtains having hot-work stability.
5. method according to claim 4, it is characterized in that: the composite catalyst of the titaniferous polynite of described step (3) carried out pre-treatment 0.5～20 hour with anhydrous hexane, heptane or toluene organic solvent earlier, and then joined in the polymerization system and mix with n-heptane solution, the organosilicon of anhydrous hexane, heptane or toluene organic solvent, ethene or propylene monomer, aluminum alkyls or aikyl aluminum halide.
6. method according to claim 4 is characterized in that: described haloalkane is dodecyl chloro alkane, tetradecyl alkyl chloride, hexadecyl chloro alkane, octadecyl chloro alkane, nonadecyl alkyl chloride, eicosyl alkyl chloride, dodecyl bromo alkane, tetradecyl bromoalkane, hexadecyl bromoalkane, octadecyl bromo alkane, nonadecyl bromoalkane, eicosyl bromoalkane, dodecyl idoalkane, tetradecyl idoalkane, hexadecyl idoalkane, octadecyl iodo alkane, nonadecyl idoalkane or eicosyl idoalkane.
7. method according to claim 4 is characterized in that: described magnesium halogenide is MgCl
2, MgBr
2Or MgI
2
8. method according to claim 4 is characterized in that: described titanium compound is TiCl
1, TiBr
4Or TiI
4
9. method according to claim 4 is characterized in that: described alcohol is butanols, sec-n-octyl alcohol, 1-octanol or isooctyl alcohol.
10. method according to claim 4 is characterized in that: described acid anhydrides is Tetra hydro Phthalic anhydride, trimellitic anhydride or Pyroglutaric acid.
11. according to claim 4 or 5 described methods, it is characterized in that: described organosilicon molecular formula is: R
nSi (OR ')
4-nWherein to represent carbonatoms be C for R or R '
1～C
8Alkane or aromatic hydrocarbon, 0≤n≤3.
12. according to claim 4 or 5 described methods, it is characterized in that: described aluminum alkyls is triethyl aluminum or triisobutyl aluminium; Aikyl aluminum halide is dimethyl monochlor(in)ate aluminium, monomethyl al dichloride, diethyl monochlor(in)ate aluminium, an ethylaluminum dichloride, diisobutyl monochlor(in)ate aluminium or an isobutyl-al dichloride.
13. the purposes according to each described material of claim 1～3 is characterized in that: described polyolefine/alkyl phosphate modified montmorillonite nano compound material is used to prepare the material of automotive industry component, plastic film for agricultural use, packing, motion goods, electrical component.
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| WO2004063268A1 (en) * | 2003-01-15 | 2004-07-29 | Ciba Specialty Chemicals Holding Inc. | Stabilization of thermoplastic nanocomposites |
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| WO2004063268A1 (en) * | 2003-01-15 | 2004-07-29 | Ciba Specialty Chemicals Holding Inc. | Stabilization of thermoplastic nanocomposites |
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| Anticorrosively Enhanced PMMA-Clay NanocompositeMaterials with Quaternary Alkylphosphonium Salt as anIntercalating Agent. Yeh, Jui-Ming, etc.Chemistry of Materials,Vol.14 No.1. 2002 * |
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