CN104841358B - A kind of preparation method of polyolefin hydrotalcite acid-acceptor - Google Patents
A kind of preparation method of polyolefin hydrotalcite acid-acceptor Download PDFInfo
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- CN104841358B CN104841358B CN201510226827.9A CN201510226827A CN104841358B CN 104841358 B CN104841358 B CN 104841358B CN 201510226827 A CN201510226827 A CN 201510226827A CN 104841358 B CN104841358 B CN 104841358B
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- hydrotalcite
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Abstract
The invention discloses a kind of preparation method of the more excellent polyolefin hydrotalcite acid-acceptor of the performance for belonging to polyolefin auxiliary agent preparing technical field.This method is that solvable divalent metal salt, solvable trivalent metal salt, urea are added into organic solvent, or the in the mixed solvent of water and organic solvent, crystallization at a certain temperature in autoclave is moved into, centrifuge washing after the completion of reaction, is drying to obtain polyolefin hydrotalcite acid-acceptor.The present invention adds organic solvent when hydrotalcite synthesizes, the factor such as different solubility, solvent viscosity increase influences hydrotalcite crystal growth to metal ion in organic solvent, final hydrotalcite crystalline structure growth is imperfect, surface has more acid adsorption potentials, and chemical adsorption capacity of the hydrotalcite to chlorion is greatly improved.So that sour effect is preferably inhaled in having when polyolefin synthesizes for hydrotalcite, its stability is improved.Hydrotalcite is not easy to separate out in resin simultaneously, eliminates corrosion of the metal stearate salt form acid-acceptor residual for production equipment.
Description
Technical field
The invention belongs to polyolefin auxiliary agent preparing technical field, and in particular to a kind of more excellent polyolefin neatly of performance
The preparation method of stone acid-acceptor.
Background technology
The polyolefin Ziegler-Natta catalyst that uses of synthesis and radical initiator can reduce side reaction and more
Obtain the less product of side chain well, but due to being deposited on CaCl with the chloride of titanium more than Ziegler-Natta catalyst2Knot
Brilliant or SiO2On carrier, this can cause to remain a small amount of chlorine-containing compound in product, in addition other additive (mainly brominated resistances
Combustion agent) other acid impurities can be also remained in process of production, these residues can make product made of polymer long-term
It also occur that changing colour and damaging during use, while chlorion or common corrosive ion, easily cause stainless steel
Corrosion, damages to production equipment and pipeline.The removal of conventional metal stearate salt acid-acceptor can cause on a small quantity
Calcium stearate is remained on the inwall of process equipment, and calcium stearate can generate stearic acid vapour under conditions of heated, cause to set
The corrosion of standby inwall.
The content of the invention
To solve above-mentioned the problems of the prior art, the present invention provides a kind of polyolefin of excellent performance and inhales acid with hydrotalcite
Agent and preparation method thereof.Acid-acceptor produced by the present invention, which can provide, preferably inhales acid energy, makes polyolefin stability more longlasting,
And reduce the corrosion and destruction of production equipment and pipeline caused by residues of chloride.
The technical scheme is that：Solvable divalent metal salt, solvable trivalent metal salt, urea are added into organic solvent,
Or the in the mixed solvent of water and organic solvent, move into crystallization at a certain temperature in autoclave, after the completion of reaction centrifugation wash
Wash, be drying to obtain polyolefin hydrotalcite acid-acceptor.
The preparation method of hydrotalcite acid-acceptor of the present invention is：By solvable divalent metal salt, solvable trivalent metal salt,
Urea addition organic solvent or the in the mixed solvent of water and organic solvent, wherein bivalent metal ion and trivalent metal ion
The ratio between amount of material is 1:1-5:1, the concentration of bivalent metal ion is 0.0001-2mol/L, and the addition of urea is divalence gold
Belong to 2-5 times of the molal quantity sum of ion and trivalent metal ion；Reaction temperature is 90 DEG C -200 DEG C；Reaction time is 1-
108h；Centrifuge washing after the completion of reaction, it is drying to obtain hydrotalcite acid-acceptor.
Described solvable divalent metal salt and solvable trivalent metal salt are villaumite, nitrate or sulfate.
Described bivalent metal ion is selected from Mg2+、Zn2+、Ca2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+、Be2+In
One or two, preferably Mg2+、Zn2+、Ca2+、Ni2+One or both of；Trivalent metal ion is selected from Al3+、Ni3+、Co3+、
Fe3+、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+One or both of, preferably Al3+、Ni3+、Fe3+One or both of.
One or more of the described organic solvent in methanol, ethanol, ethylene glycol, glycerine, acetone, ether.
The above-mentioned hydrotalcite acid-acceptor being prepared is applied in polyolefin synthesis.
Described polyolefin is polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, second
Alkene-acrylate copolymer, propylene acrylic acid copolymer, poly 1-butene, poly(4-methyl-1-pentene), cyclic olefin polymer.
The present invention adds organic solvent when hydrotalcite synthesizes, metal ion different solubility, solvent in organic solvent
The factors such as viscosity increase influence hydrotalcite crystal growth, and final hydrotalcite crystalline structure growth is imperfect, and surface has more polyacid
Property adsorption potential, is greatly improved chemical adsorption capacity of the hydrotalcite to chlorion.So that hydrotalcite when polyolefin synthesizes
With sour effect is preferably inhaled, its stability is improved.The organic solvent that the present invention uses is mostly nontoxic or less toxic, to environment without mistake
Major injury.
The present invention cleans polyolefin acid-acceptor using hydrotalcite as one kind, and the layer structure and loose structure of hydrotalcite can
The acidic materials of effective absorbing catalyst residual, the chlorion particularly remained, improve polyolefin stability, with common synthesis side
Method obtains hydrotalcite and compared, and this method has the acid energy of stronger suction and long-time stability.Hydrotalcite is not easy in resin simultaneously
Separate out, eliminate corrosion of the metal stearate salt form acid-acceptor residual for production equipment, and the acid-acceptor low toxic and environment-friendly, meet
The requirement of current green production.The preparation method of the present invention is simple, and raw material sources are extensive, technological process and its simple, and inhales acid
Performance significantly improves.
Embodiment
Embodiment 1
Organic solvent/water mixed solvent synthesizes Mg-Al hydrotalcites as polyolefin acid-acceptor：
By Mg (NO3)2、Al(NO3)3With urea according to Mg2+/Al3+Mol ratio is 2:1, Urea/ (Mg2++Al3+Rub)=2
Your ratio is made into ethanol/water mixed solution, and wherein the ratio between amount of material of ethanol/water is 1：3；, Mg2+Concentration is 0.6mol/L.
Mixed solution is moved into closed reactor, next crystallization 24h obtains CO at 90 DEG C3- LDHs slurries, naturally cool to room
Temperature, slurries are obtained into LDHs filter cakes after washing centrifugation to supernatant liquor is neutrality, and filter cake is done in 60 DEG C of baking oven
Dry 10h, obtains the magnalium hydrotalcite acid-acceptor for polyolefin after grinding, its structural formula is [Mg0.66Al0.33(OH)2]
(CO3)0.16·H2O。
The magnalium hydrotalcite acid-acceptor of preparation is added in polypropylene powder, the addition of magnalium hydrotalcite acid-acceptor is
500ppm, extruded in double screw extruder, screw temperature set TS1：180 DEG C, TS2-TS10：200 DEG C, by three times
Extrusion, the polypropylene yellow colour index for extruding test three times is respectively 1.7,3.8 and 6.3.
Comparative example 1
Water is that solvent synthesizes Mg-Al hydrotalcites as polyolefin acid-acceptor：
By Mg (NO3)2、Al(NO3)3With urea according to Mg2+/Al3+Mol ratio is 2:1, Urea/ (Mg2++Al3+Rub)=2
That ratio obtained aqueous solution, wherein, Mg2+Concentration is 0.6mol/L.Solution is moved into closed reactor, next at 90 DEG C
Crystallization 24h obtains CO3- LDHs slurries, naturally cool to room temperature, by slurries after washing centrifugation to supernatant liquor is neutrality
10h is dried in 60 DEG C of baking oven to LDHs filter cakes, and by filter cake, obtains inhaling acid for the magnalium hydrotalcite of polyolefin after grinding
Agent, its structural formula are [Mg0.66Al0.33(OH)2](CO3)0.16·H2O。
The magnalium hydrotalcite acid-acceptor of preparation is added in polypropylene powder, the addition of magnalium hydrotalcite acid-acceptor is
500ppm, extruded in double screw extruder, screw temperature set TS1：180 DEG C, TS2-TS10：200 DEG C, by three times
Extrusion, the polypropylene yellow colour index for extruding test three times is respectively 2.3,4.8 and 8.1.
Embodiment 2
Organic solvent/water mixed solvent synthesizes Zn-Al hydrotalcites as polyolefin acid-acceptor：
By Zn (NO3)2、Al(NO3)3With urea according to Zn2+/Al3+Mol ratio is 2:1, Urea/ (Zn2++Al3+Rub)=5
Your ratio prepares ether/aqueous solution, and wherein the ratio between amount of material of ether/water is 1：3, Zn2+Concentration is 0.6mol/L.By solution
Move into closed reactor, next crystallization 24h obtains CO at 90 DEG C3- LDHs slurries, naturally cool to room temperature, by slurries
LDHs filter cakes are obtained after washing centrifugation to supernatant liquor is neutrality, and filter cake is dried into 10h, grinding in 60 DEG C of baking oven
The zinc-aluminum hydrotalcite acid-acceptor for polyolefin is obtained afterwards, and its structural formula is [Zn0.66Al0.33(OH)2](CO3)0.16·H2O。
The zinc-aluminum hydrotalcite acid-acceptor of preparation is added in polypropylene powder, the addition of zinc-aluminum hydrotalcite acid-acceptor is
500ppm, extruded in double screw extruder, screw temperature set TS1：180 DEG C, TS2-TS10：200 DEG C, by three times
Extrusion, the polypropylene yellow colour index for extruding test three times is respectively 1.2,3.0 and 5.8.
Comparative example 2
Water is that solvent synthesizes Zn-Al hydrotalcites as polyolefin acid-acceptor：
By Zn (NO3)2、Al(NO3)3With urea according to Zn2+/Al3+Mol ratio is 2:1, Urea/ (Zn2++Al3+Rub)=5
That ratio obtained aqueous solution, wherein, Zn2+Concentration is 0.6mol/L.Solution is moved into closed reactor, next at 90 DEG C
Crystallization 24h obtains CO3- LDHs slurries, naturally cool to room temperature, by slurries after washing centrifugation to supernatant liquor is neutrality
10h is dried in 60 DEG C of baking oven to LDHs filter cakes, and by filter cake, obtains inhaling acid for the zinc-aluminum hydrotalcite of polyolefin after grinding
Agent, its structural formula are [Zn0.66Al0.33(OH)2](CO3)0.16·H2O。
The zinc-aluminum hydrotalcite acid-acceptor of preparation is added in polypropylene powder, the addition of zinc-aluminum hydrotalcite acid-acceptor is
500ppm, extruded in double screw extruder, screw temperature set TS1：180 DEG C, TS2-TS10：200 DEG C, by three times
Extrusion, the polypropylene yellow colour index for extruding test three times is respectively 2.5,4.6 and 7.7.
Drawn by above-mentioned contrast test, organic solvent/water mixed solvent synthetic hydrotalcite can be effective as acid-acceptor
The acidic materials of absorbing catalyst residual, improve the stability of polyolefin.Embodiment 1 and embodiment 2 are with mixed solvent synthetic water
Talcum is significantly carried as the effect of acid-acceptor than the effect only by the use of water as solvent synthetic hydrotalcite as acid-acceptor
Rise.
Claims (4)
- A kind of 1. application of hydrotalcite acid-acceptor in polyolefin synthesis, it is characterised in that the preparation of the hydrotalcite acid-acceptor Method is：Solvable divalent metal salt, solvable trivalent metal salt, urea are added to the mixing of organic solvent or water and organic solvent In solvent, wherein the ratio between amount of material of bivalent metal ion and trivalent metal ion is 1:1-5:1, bivalent metal ion it is dense It is the 2-5 of the molal quantity sum of bivalent metal ion and trivalent metal ion to spend for 0.0001-2mol/L, the addition of urea Times；Reaction temperature is 90 DEG C -200 DEG C；Reaction time is 1-108h；Centrifuge washing after the completion of reaction, it is drying to obtain hydrotalcite suction Sour agent；One or more of the described organic solvent in methanol, ethanol, ethylene glycol, glycerine, acetone, ether.
- 2. application according to claim 1, it is characterised in that described solvable divalent metal salt and solvable trivalent metal salt For villaumite, nitrate or sulfate.
- 3. application according to claim 1, it is characterised in that described bivalent metal ion is selected from Mg2+、Zn2+、Ca2+、 Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cd2+、Be2+One or both of；Trivalent metal ion is selected from Al3+、Ni3+、Co3+、Fe3 +、Mn3+、Cr3+、V3+、Ti3+、In3+、Ga3+One or both of.
- 4. application according to claim 1, it is characterised in that described polyolefin is polyethylene, polypropylene, ethene-vinegar Sour ethylene copolymer, ethylene-acrylic acid copolymer, vinyl-acrylate copolymer, propylene acrylic acid copolymer, poly- 1- fourths Alkene, poly(4-methyl-1-pentene), cyclic olefin polymer.
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| Title |
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| 混合溶剂制备Mg/Al水滑石;贺娟等;《硅酸盐学报》;20091231;第37卷(第12期);第2061-2065页 * |
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