CN101321692B - Process for preparing organically modified layered double hydroxide - Google Patents
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- CN101321692B CN101321692B CN2006800457383A CN200680045738A CN101321692B CN 101321692 B CN101321692 B CN 101321692B CN 2006800457383 A CN2006800457383 A CN 2006800457383A CN 200680045738 A CN200680045738 A CN 200680045738A CN 101321692 B CN101321692 B CN 101321692B
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Abstract
The invention relates to a process for preparing an organically modified layered double hydroxide having a distance between the individual layers of the layered double hydroxide of above 1.5 nm and comprising an organic anion as charge-balancing anion, the process comprising the steps of: (a) preparing a precursor suspension comprising a divalent metal ion source and a trivalent metal ion source; (b) solvothermally treating the precursor suspension to obtain the layered double hydroxide, wherein an organic anion is added before or during the formation of the layered double hydroxide of step (b), or following the formation of the layered double hydroxide, so as to obtain the organically modified layered double hydroxide, with the proviso that deoxycholic acid is not the sole organic anion.; The invention further pertains to a process for preparing an organically modified layered double hydroxide having a distance between the individual layers of the layered double hydroxide of above 1.5 nm and comprising an organic anion as charge-balancing anion, the process comprising the steps of: (a) preparing a precursor suspension comprising a divalent metal ion source and a trivalent metal ion source; (b) thermally treating the precursor suspension to obtain the layered double hydroxide, wherein an organic anion is added before or during the formation of the layered double hydroxide of step (b), or following the formation of the layered double hydroxide, so as to obtain the organically modified layered double hydroxide, with the proviso that in step a) the trivalent metal ion source is not reacted with the organic anion at a temperature of between 60 and 85 DEG C for 4 to 8 hours prior to the addition of the divalent metal ion source and step b) is subsequently carried out at a temperature of 90 to 95 DEG C for 4 to 8 hours.
Description
The present invention relates to prepare the method for organically-modified layered double-hydroxide.
These class methods are known in this area.
WO 99/35185 discloses the method for preparing organically-modified layered double-hydroxide (LDH), wherein through IX LDH is introduced in organic anion.Through LDH being suspended in the water and subsequently the pH of suspension-s being reduced to the value less than 4, carry out this IX.Then, organic anion is added into suspension-s, and with pH regulator to the value that is higher than 8.This method is quite complicated, produces saliniferous waste liquid stream usually.
WO 00/09599 has described and has comprised organic anion as the preparation that embeds anionic LDH.Utilize the salt of divalence and trivalent metal ion, like the hydrochloride or the sodium aluminate of magnesium and aluminium, the LDH of these modifications can prepare in many ways.The method of describing among the WO 00/09599 needs salt, and it will finally be in the waste liquid stream at least in part, and this is undesirable.Be also noted that employed salt is expensive relatively in these methods.
In a word, aforesaid method is demonstrating aspect the economics and need more attract method friendly more on the human and environment on the economics.
Therefore, the purpose of this invention is to provide method simpler and that environment is friendly more and prepare organically-modified layered double-hydroxide.
This purpose through a kind of each interfloor distance of layered double-hydroxide for preparing greater than 1.5nm and comprise organic anion and realize that as the method for the anionic organically-modified layered double-hydroxide of charge balance this method may further comprise the steps:
(a) preparation comprises the precursor suspension of divalent metal ion source and trivalent metal ion source;
(b) solvent-thermal method (solvothermally) is handled this precursor suspension with the acquisition layered double-hydroxide,
Wherein before step (b) forms layered double-hydroxide or during forming, add organic anion; Perhaps, layered double-hydroxide adds organic anion after forming; Thereby obtain organically-modified layered double-hydroxide, prerequisite is that Septochol is not unique organic anion.
This purpose also through a kind of each interfloor distance of layered double-hydroxide for preparing greater than 1.5nm and comprise organic anion and realize that as the method for the anionic organically-modified layered double-hydroxide of charge balance this method may further comprise the steps:
(a) preparation comprises the precursor suspension of divalent metal ion source and trivalent metal ion source;
(b) this precursor suspension of thermal treatment to be obtaining layered double-hydroxide,
Wherein, Before step (b) forms layered double-hydroxide or during forming, add organic anion; Perhaps, layered double-hydroxide adds organic anion after forming; Thereby obtain organically-modified layered double-hydroxide, prerequisite be in the step (a) before adding divalent metal ion source 4-8 hour trivalent metal ion source under 90-95 ℃, do not carrying out 4-8 hour subsequently under 60-85 ℃ the temperature with organic anion reaction and step (b).
Divalent metal ion source and trivalent metal ion source with in the methods of the invention are not the salt of these metals ions; Especially these sources are not the muriate or the perchlorate of divalence and trivalent metal ion, if perhaps trivalent metal ion is aluminium then is not aluminate.It should be noted that these sources can be partly dissolved in suspension medium.Divalence and trivalent metal ion source are generally the oxide compound or the oxyhydroxide of divalence or trivalent metal ion.The instance of divalent-metal ion is Zn
2+, Mn
2+, Ni
2+, Co
2+, Fe
2+, Cu
2+, Sn
2+, Ba
2+, Ca
2+And Mg
2+The instance of trivalent metal ion is Al
3+, Cr
3+, Fe
3+, Co
3+, Mn
3+, Ni
3+, Ge
3+And Ga
3+Also can consider in the layered double-hydroxide of the inventive method preparation, to use three kinds or more kinds of different metallic ion.In these metals ions, preferred Mg
2+And/or Zn
2+And Al
3+Combination.The instance in the magnesium source that is fit to comprises Natural manganese dioxide, Marinco H, magnesium basic carbonate, Magnesium hydrogen carbonate, rhombspar and sepiolite.Preferred Natural manganese dioxide.Also can consider the combination in two kinds or more kinds of magnesium source.The aluminium source is generally the oxyhydroxide or the oxide compound of aluminium.The instance in this aluminium source is three white lakes such as gipsite and bayerite, and peroxo-aluminium (Aluminium oxohydroxide) is like boehmite, diaspore or pyrrhosiderite, and transition alumina, and these are known for a person skilled in the art.
The use of above-mentioned divalent-metal ion and trivalent metal ion source provides environment friendly more method in the inventive method, even owing to the words that also have also are that quite few salt remains in the waste liquid stream of this method generation.In addition, divalence and trivalent metal ion source, especially magnesium and aluminium source, more cheap than the corresponding salt that is usually used in production of layered double hydroxides usually.In addition, method of the present invention is simpler usually, because its aftertreatment that needs step still less and/or do not need waste liquid stream.In addition, these methods can be carried out the significantly shorter time, and it can reach the organically-modified layered double-hydroxide productive rate higher than ordinary method then.
In an embodiment of the inventive method, before thermal treatment or solvent heat treatment comprise the suspension-s of divalent metal ion source and trivalent metal ion source, with divalent metal ion source and/or trivalent metal ion source activation.Term " activation " refers to divalence and/or trivalent metal ion source activation are increased their reactivities in the method thus; This activation can be for example realizes through dry method or wet grinding and/or through s.t..Ionogenic other advantage of activated metal is to have formed in the method the impurity of remarkable minimizing, like brucite or gipsite.The minimizing of this type impurity or do not have this type impurity to have additional advantages in the product that obtains through this method: the matrix material that can cause obtaining when in polymeric matrix, using this product has the kinetics and/or the mechanical property of improvement.
Each interfloor distance that the organically-modified layered double-hydroxide of the inventive method preparation has is greater than 1.5nm.When using these organically-modified layered double-hydroxides, for example, when in polymeric matrix, using, this has advantage.In polymeric matrix (for example in nano composite material or coating composition); Bigger interfloor distance makes layered double-hydroxide of the present invention in polymeric matrix, process easily; And further make the easy layering of layered double-hydroxide and/or peel off, obtain having modified layered double-hydroxide and the mixture of polymeric matrix of the physicals of improvement.Preferably, be 1.5nm at least, more preferably 1.6nm at least, even more preferably 1.8nm at least, and 2nm at least most preferably according to the interfloor distance among the LDH of the present invention.The distance of each interlayer can adopt X-ray diffraction and transmission electron microscope (TEM) to measure, and general introduction sees below.
In a preferred embodiment of the invention, grind before or activation divalence and/or trivalent metal ion source, especially magnesium and/or aluminium source in step (b).In the method for the invention, divalence and/or trivalent metal ion source have less than the d50 value of 20 μ m with less than the d90 value of 50 μ m usually.Preferably, the d50 value is less than 15 μ m, and the d90 value is less than 40 μ m, more preferably; The d50 value is less than 10 μ m, and the d90 value is less than 30 μ m, in addition more preferably the d50 value less than 8 μ m; And the d90 value is less than 20 μ m, and most preferably the d50 value is less than 6 μ m, and the d90 value is less than 10 μ m.Can adopt method known to those skilled in the art to measure size-grade distribution, for example according to the laser diffraction of DIN 13320.This grinding steps makes the formation of layered double-hydroxide carry out sooner.If divalence and trivalent metal ion source are magnesium and aluminium source, then it can further reduce the amount of impurity such as gipsite or brucite.
In the application's context, term " thermal treatment " and " hot method " refer under atmospheric pressure to the temperature of the boiling point of precursor suspension, handle precursor suspension at 30 ℃.If suspension medium is a water, then heat treated temperature is usually at 30 ℃ to 100 ℃, preferred 40 ℃ to 95 ℃, and most preferably 50 ℃ to 90 ℃.
In addition, term " solvent heat treatment " and " solvent-thermal method " refer to handle precursor suspension being higher than under the atmospheric pressure and under the temperature usually above this precursor suspension boiling point under atmospheric pressure.This pressure usually 1 the crust to 200 the crust, preferred 2 the crust to 150 the crust, most preferably 3 the crust to 100 the crust.If suspension medium is a water, then temperature is usually at 100 ℃ or higher, preferred 100 ℃-300 ℃, and more preferably 110 ℃-250 ℃, most preferably 120 ℃-200 ℃.
The suspension medium that is suitable for thermal treatment and solvent heat treatment simultaneously can be water, organic solvent or its mixture.The suitable instance of organic solvent comprises alcohol like methyl alcohol, ethanol, 1-propyl alcohol and Virahol, paraffinic hydrocarbons such as pentane, hexane and heptane, and aromatic hydrocarbon such as benzene, toluene and YLENE.The solvent that is particularly suitable for the inventive method is a water.
Method of the present invention can not have CO in precursor suspension
2Or carry out under any carbonate, thereby guarantee not have carbonate to be incorporated in the layered double-hydroxide as the charge balance negatively charged ion.This further makes organic anion to be incorporated in the layered double-hydroxide as the charge balance negatively charged ion.
In one embodiment of the invention, carry out in the process organic anion being added in the precursor suspension before or in step (b) in step (b).In this way, in a step, prepared organically-modified layered double-hydroxide, this makes method simpler and quicker usually, thereby more attractive at economic aspect.
Perhaps, after forming layered double-hydroxide, add organic anion, layered double-hydroxide mainly comprises hydroxyl as the charge balance negatively charged ion in this case.Saidly can easily be exchanged by organic anion as the anionic hydroxyl of charge balance.
In the application's context, term " charge balance negatively charged ion " refers to compensate the insufficient negatively charged ion of static charge of crystallization LDH lamella.Because LDH has laminate structure usually, so the charge balance negatively charged ion can be positioned on the interlayer, edge of the LDH layer that piles up (stack) or on the outside surface.This anionoid that is positioned at the interlayer of the LDH layer that piles up is called embedded ion.
This LDH that piles up or organic clay also can be for example layering or peel off in polymeric matrix.In this context, term " layering " be defined as the LDH particulate on average degree of piling up produce unit volume thus and contain the obviously more material of LDH lamella separately owing to the part layer at least of LDH structure reduces from (de-layer).Term " is peeled off " and is defined as layering completely, and promptly the periodicity on the vertical direction of LDH lamella disappears, and causes the random dispersion of each layer in medium, and making does not thus have stacking order fully.
The expansion of LDH or expansion are also referred to as the embedding of LDH, can pass through X-ray diffraction (XRD) and observe, because basal reflex is that the position that d (00l) reflects is the demonstration of interfloor distance, this distance increases with embedding.
On average the reduction of degree of piling up can be with the widening or observe until disappearance of XRD reflection, and perhaps the increase of the asymmetry through basal reflex (00l) is observed.
The sign that complete layering is promptly peeled off is still analytical challenge, but can judge from the completely dissolve of original LDH non-(hk0) reflection usually.
Can further observe layer order through transmission electron microscope (TEM), and then, degree of layering.
LDH of the present invention can be any LDH well known by persons skilled in the art.Usually, these LDH are for can expand or expansible mineral LDH.This type LDH has the laminate structure that comprises charged crystalline sheets (being also referred to as each LDH layer), accompanies the charge balance negatively charged ion therein.Term in the application's context " expansion " and " expansion " refer to that the distance between charged crystalline sheets increases.Distensible LDH can expand in solvent that is fit to such as water, and through the modification with other (organic) charge balance ion exchange charge counterion, this modification is also referred to as embedding in the art.
Organically-modified layered double-hydroxide of the present invention has the laminate structure of corresponding following general formula:
[M
m 2+M
n 3+(OH)
2m+2n]X
n/z z-·bH
2O (I)
Wherein, M
2+Be divalent-metal ion, like Zn
2+, Mn
2+, Ni
2+, Co
2+, Fe
2+, Cu
2+, Sn
2+, Ba
2+, Ca
2+, Mg
2+, M
3+Be trivalent metal ion, like Al
3+, Cr
3+, Fe
3+, Co
3+, Mn
3+, Ni
3+, Ce
3+And Ga
3+, the value of m and n should make m/n=1-10, and the value of b is in the scope of 0-10.X is the charge balance organic anion with at least 8 carbon atoms, or other negatively charged ion well known by persons skilled in the art, as long as at least a portion of this embedded ion is the organic anion with at least 8 carbon atoms.
Other anionic instance known in the art comprises oxyhydroxide, carbonate, supercarbonate, nitrate salt, muriate, bromide, sulphonate, vitriol, hydrosulfate, vannadate, tungstate, borate, phosphoric acid salt, column (pillaring) negatively charged ion such as HVO
4 -, V
2O
7 4-, HV
2O
12 4-, V
3O
9 3-, V
10O
28 6-, Mo
7O
24 6-, PW
12O
40 3-, B (OH)
4 -, B
4O
5(OH)
4 2-, [B
3O
3(OH)
4]
-, [B
3O
3(OH)
5]
2-, HBO
4 2-, HGaO
3 2-, CrO
4 2-And Keggin ion.
LDH of the present invention comprises hydrotalcite and hydrotalcite-like anionic LDH.The instance of this type LDH is hydrotalcite and houghite material; Hydroxyl pyrope (meixnerite); Manasseite (manasseite), pyroaurite (pyroaurite), sjogrenite
; Stichtite (stichtite); Barberonite, takovite (takovite), reevesite (reevesite) and hydroxyl carbon manganese magnesite (desautelsite).Preferred LDH is a hydrotalcite, and it is the LDH that has corresponding to the laminate structure of following general formula:
[Mg
m 2+Al
n 3+(OH)
2m+2n]X
n/z z-·bH
2O (II)
Wherein the value of m and n should make m/n=1-10, and preferably 1-6, and the value of b is generally the value of 2-6 in the scope of 0-10, and often is about 4 value.X is definition charge balance ion as above.
Preferred m/n should be the value of 2-4, more particularly near 3 value.
Any crystalline form that LDH can be known in the art, for example people such as people's (CatalysisToday, 11 (1991), the 173-301 page or leaf) such as Cavani or Bookin (LDHs and LDH Minerals, (1993), the mat woven of fine bamboo strips 41 (5) volumes, 558-564 page or leaf) are described.If this LDH is a hydrotalcite, then this hydrotalcite can be for having for example 3H
1, 3H
2, 3R
1Or 3R
2The polytype of piling up.
Organic anion with in the methods of the invention can be any organic anion that produces the organically-modified layered double-hydroxide of the present invention through embedding.Organic anion applicable to this method can be from the salt or the acid of organic anion.Organic anion such as stearic an alkali metal salt that use comes from salt can be favourable, because it is compared with the corresponding organic anion that comes from acid better solvability are arranged in solvent.Perhaps, it can be favourable using the organic anion that comes from acid, because can in waste liquid stream, not introduce salt ion, the stream that do not need like this to dispose waste liquid is in addition removed salt ion, makes this method more cheap and simpler.
The organo-metallic negatively charged ion that is suitable for the inventive method comprises 8 or more carbon atoms usually, and prerequisite is that terephthaldehyde's acid group is not the unique organic anion that exists as the charge balance negatively charged ion.That the organic anion that this type has at least 8 carbon atoms comprises is single-, two-or poly carboxylic acid root, sulfonate radical, phosphonate radical and sulfate radical.Preferably, this organic anion comprises at least 10 carbon atoms, more preferably at least 12 carbon atoms; And this organic anion comprises at the most 1; 000 carbon atom, preferred 500 carbon atoms at the most, more preferably 100 carbon atoms at the most; Even more preferably 50 carbon atoms at the most, most preferably 20 carbon atoms at the most.Consider to use 2 kinds or more kinds of organic anion, wherein one of at least have at least 8 carbon atoms, and resulting LDH has the interfloor distance of 1.5nm at least; One of other organic anion can have thus and is less than 8 carbon atoms.
It is not too preferred only comprising a kind of organically-modified LDH that is selected from the charge balance organic anion of acetate, amber acid radical, benzoate anion and terephthaldehyde's acid group; Because they have the interfloor distance less than 1.5nm; And in polymeric matrix, be not easy usually to peel off or layering, make the LDH of these modifications not too be suitable for for example nano composite material or coating composition.The instance of the LDH that this type is organically-modified is at US 5,728, provides in 366.In addition, also be not too preferred with Septochol as unique organic anion, because it is too expensive.In addition, Septochol contains two oh groups, this possibly cause in polymeric matrix peel off or layering very the difficulty or even maybe.It is believed that this be because the interaction between two kinds or the more kinds of embedding Septochol negatively charged ion or since the column behavior that the interaction of the single Septochol negatively charged ion clay platelet different with two kinds causes cause.In one embodiment of the invention, do not hope that Septochol is used as the charge balance negatively charged ion.
Consider that also the charge balance organic anion comprises one or more functional groups, for example hydroxyl, amine, carboxylic acid and vinyl.If the LDH that this type is organically-modified is used in the polymeric matrix, then this type functional group can with interpolymer interaction or reaction.
The suitable instance of organic anion of the present invention is a monocarboxylic acid, for example lipid acid and based on the rosiny ion.
In one embodiment, organic anion is to have the lipid acid of 8-22 carbon atom or its salt.This lipid acid can be saturated or unsaturated fatty acids.The suitable instance of this type lipid acid is sad, capric acid, LAURIC ACID 99 MIN, tetradecanoic acid, palmitinic acid, Triple Pressed Stearic Acid, eicosanoic acid, decylenic acid, Zoomeric acid, oleic acid, linolic acid, linolenic acid and composition thereof.
In another embodiment of the present invention, organic anion is rosin or its salt.Rosin is from natural origin, obtains easily and compares relatively inexpensive with synthetic organic anion.The representative instance of rosiny natural origin is rosin, wood rosin and starex.The normally various monocarboxylic acid three that contains 20 carbon atoms of having an appointment usually of rosin encircles the suspension-s of the different isomerization body of sylvic acids.The tricyclic structure of different sylvic acids is mainly different on position of double bond.Usually, rosin is the suspension-s of some materials, and these materials comprise levopimaric acid, neoabietic acid, palustric acid, abietic acid, dehydroabietic acid, disconnected dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, pimaric acid and isopimaric acid.Rosin from natural origin also comprises through polymerization, isomerizing, disproportionation, hydrogenation and the rosin of the remarkable modification of quilt, i.e. rosin suspension-s with Diels-Alder (Diels-Alder) reaction of vinylformic acid, acid anhydrides and propenoate.The product that obtains through these methods is called modified rosin.Natural rosin also can carry out chemically changed through any method known in the art, and for example carboxylic group on the rosin and MOX, metal hydroxides or reactant salt are to form rosined soap or salt (so-called tallate).The rosin of this type chemically changed is called rosin derivative.
Can be through introducing organic group, anionic group or cation group with this Abietyl modified or chemically changed.Organic group can be for having the substituted or unsubstituted aliphatic series or the aromatic hydrocarbon of 1-40 carbon atom.This anionic group can be any anionic group well known by persons skilled in the art, for example carboxylate radical or sulfonate radical.
These further details based on the rosiny material can be from D.F.Zinkel and J.Russell (Naval Stores, production-chemistry-utilization, 1989; New York, part ii, the 9th chapter) and J.B.Class (" Resins; Natural; " The 1st chapter: " Rosin and ModifiedRosins, " Kirk-Othmer Encyclopedia of Chemical Technology, announce the time: on December 4th, 2000) collect on the net.
Also consider to use the LDH that comprises one or more organic anions of the present invention.In one embodiment, this embedding negatively charged ion is lipid acid and rosiny mixture.
Usually, at least 10% of the embedded ion total amount for organic anion in LDH type of the present invention, preferred embedded ion total amount at least 30%, more preferably at least 60%, and most preferably at least 90% be organic anion.In preferred embodiments; Embed at least 10% of negatively charged ion total amount and be fatty acid source or based on the rosiny negatively charged ion; Perhaps these two kinds of anionic suspension-s; Preferred embedded ion total amount at least 30%, more preferably at least 60%, and most preferably at least 90% be fatty acid source or based on the rosiny negatively charged ion, perhaps these two kinds of anionic mixtures.
In following examples, further set forth the present invention.
Embodiment
Embodiment 1
The state of commercial lipid acid when receiving uses.Kortacid
PH05 (palmitinic acid and stearic mixture) is provided by the Oleochemicals GmbH of a company of Akzo Nobel Chemicals.
Natural manganese dioxide (Zolitho with 50g
40, available from Martin Marietta MagnesiaSpecialties LLC) and three white lakes (Alumill F505) of 39g in the softening water of 648g, mix and be ground to mean particle size (d
50) be 2.5 μ m.This slurry adding is equipped with in the oily thermal high still of high speed agitator, and is heated to 80 ℃.Follow 15 minutes adding autoclaves of Kortacid
PH05 warp with 102g.Before adding, fatty acid blend is heated to 80 ℃.After acid adds, close autoclave and be heated to 170 ℃, kept 1 hour.Then autoclave is cooled to about 40 ℃, takes out the slurry that obtains.Then with this slurry with 2, centrifugal about 10 minutes of 000rpm.Pour out liquid, and under 80 ℃ in baking oven under vacuum drying solid spend the night.
Analyze the resulting hydrotalcite-like clay that comprises fatty acid blend through X-ray diffraction, to confirm interlamellar spacing (inter-gallery spacing) or d-spacing.As above the XRD figure case of the hydrotalcite-like clay of preparation has shown little hydrotalcite relevant non-(hk0) reflection, and the embedding of anionic clay has been described.This embedding has shown characteristic d (00l) value
Embodiment 2
Through the fused oil rosin (Chinese gum rosin) and the stable rosin that has been heated 235 ℃ and internal pair production.Vultac
-2 (ArkemaInc.) that added rosiny 3.5 weight % during the fusion.Fused rosin was stirred 15 hours down at 235 ℃, subsequently resin is cooled off for use.Natural manganese dioxide (Zolitho with 50g
40, available from Martin Marietta MagnesiaSpecialties LLC) and three white lakes (Alumill F505) of 39g in the softening water of 648g, mix and be ground to mean particle size (d
50) be 2.5 μ m.This slurry added be equipped with in the oily thermal high still of high speed agitator, at its sealing post-heating to 120 ℃.The rosin of the 115g stabilization that then will as above prepare was through 30 minutes adding autoclaves.Before the adding, rosin blend also is heated to 120 ℃.After acid adds, autoclave is heated to 170 ℃, kept 1 hour.Then autoclave is cooled to about 40 ℃, takes out the slurry that obtains.Then with this slurry with 2, centrifugal about 10 minutes of 000rpm.Pour out liquid, and under 80 ℃ in baking oven under vacuum drying solid spend the night.
Analyze the resulting hydrotalcite-like clay that comprises fatty acid blend through X-ray diffraction, to confirm interlamellar spacing (inter-gallery spacing) or d-spacing.As above the XRD figure case of the hydrotalcite-like clay of preparation has shown little hydrotalcite relevant non-(hk0) reflection, and the embedding of anionic clay has been described.This embedding has shown characteristic d (00l) value
Embodiment 3
Natural manganese dioxide (Zolitho with 252g
40, available from Martin Marietta MagnesiaSpecialties LLC) and three white lakes (Alumill F505) of 240g 3, mix in the softening water of 513g and be ground to mean particle size (d
50) be 2.4 μ m.A part (704g) adding of this slurry has been equipped with in the glass reactor of whisking appliance, nitrogen gas stream and reflux cooler.This slurry is heated to 90 ℃.Then 147g fused Kortacid PH05 (T=90 ℃) is added in this glass reactor through 90 minutes.Reaction mixture was kept 19 hours in 90 ℃ again, be cooled to then below 50 ℃.Then with the slurry that obtains with 2, centrifugal about 10 minutes of 000rpm.Pour out liquid, and under 80 ℃ in baking oven under vacuum drying solid spend the night.
Analyze the resulting hydrotalcite-like clay that comprises fatty acid blend through X-ray diffraction, leave or the d-spacing to confirm interlamellar spacing (inter-gallery spacing).As above the XRD figure case of the hydrotalcite-like clay of preparation has shown little hydrotalcite relevant non-(hk0) reflection, and the embedding of anionic clay has been described.This embedding has shown characteristic d (00l) value
Claims (11)
1. one kind prepares each interfloor distance of layered double-hydroxide greater than 1.5nm and comprise the method for organic anion as the anionic organically-modified layered double-hydroxide of charge balance, said method comprising the steps of:
(a) preparation comprises the precursor suspension of divalent metal ion source and trivalent metal ion source;
(b) solvent-thermal method is handled said precursor suspension with the acquisition layered double-hydroxide,
Wherein before step (b) forms layered double-hydroxide or during forming, add organic anion; Perhaps, layered double-hydroxide adds organic anion after forming; Thereby obtain organically-modified layered double-hydroxide; And wherein said organic anion has 8 or more a plurality of carbon atom, and prerequisite is that terephthaldehyde's acid group is not the unique organic anion that exists as the charge balance negatively charged ion, and wherein water is as suspension medium; And wherein grind said divalent metal ion source and/or said trivalent metal ion source before in step (b)
Prerequisite is that Septochol is not unique organic anion,
Wherein said solvent-thermal method refers to handle precursor suspension being higher than under the atmospheric pressure and being higher than under the temperature of said precursor suspension boiling point under atmospheric pressure.
2. one kind prepares each interfloor distance of layered double-hydroxide greater than 1.5nm and comprise the method for organic anion as the anionic organically-modified layered double-hydroxide of charge balance, said method comprising the steps of:
(a) preparation comprises the precursor suspension of divalent metal ion source and trivalent metal ion source;
(b) the said precursor suspension of thermal treatment to be obtaining layered double-hydroxide,
Wherein, Before step (b) forms layered double-hydroxide or during forming, add organic anion; Perhaps after layered double-hydroxide forms, add organic anion, thereby obtain organically-modified layered double-hydroxide, and wherein said organic anion has 8 or more a plurality of carbon atom; Prerequisite is that terephthaldehyde's acid group is not the unique organic anion that exists as the charge balance negatively charged ion; Prerequisite is not react with said organic anion under 60-85 ℃ temperature in 4-8 hour before said trivalent metal ion source of the said divalent metal ion source of interpolation in the step (a), and step (b) was carried out under 90-95 ℃ temperature 4-8 hour subsequently
Wherein water is used as suspension medium, and wherein grinds said divalent metal ion source and/or said trivalent metal ion source before in step (b),
Wherein said thermal treatment refers under atmospheric pressure to the temperature of the boiling point of said precursor suspension, handle said precursor suspension at 30 ℃.
3. according to the method for claim 1 or 2, wherein carrying out step (b) before with said organic anion adding precursor aqeous suspension.
4. according to the method for claim 1 or 2, wherein after layered double-hydroxide forms, add said organic anion, wherein said layered double-hydroxide mainly has hydroxyl as the charge balance negatively charged ion.
5. according to the method for claim 1 or 2, wherein said divalent-metal ion is Mg
2+With trivalent metal ion be Al
3+
6. according to the method for claim 3, wherein said divalent-metal ion is Mg
2+With trivalent metal ion be Al
3+
7. according to the method for claim 4, wherein said divalent-metal ion is Mg
2+With trivalent metal ion be Al
3+
8. according to the method for claim 1 or 2, the d50 value of wherein said divalent metal ion source and/or trivalent metal ion source is less than 10 μ m.
9. according to the method for claim 6 or 7, the d50 value of wherein said divalent metal ion source and/or trivalent metal ion source is less than 10 μ m.
10. according to the method for claim 1 or 2, wherein said organic anion has 10-40 carbon atom.
11. according to the method for claim 9, wherein said organic anion has 10-40 carbon atom.
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| Application Number | Priority Date | Filing Date | Title |
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| EP05111752 | 2005-12-06 | ||
| EP05111752.1 | 2005-12-06 | ||
| US75120605P | 2005-12-19 | 2005-12-19 | |
| US60/751,206 | 2005-12-19 | ||
| PCT/EP2006/069204 WO2007065859A1 (en) | 2005-12-06 | 2006-12-01 | Process for preparing organically modified layered double hydroxide |
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| CN101321692A CN101321692A (en) | 2008-12-10 |
| CN101321692B true CN101321692B (en) | 2012-08-22 |
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| CN2006800457383A Expired - Fee Related CN101321692B (en) | 2005-12-06 | 2006-12-01 | Process for preparing organically modified layered double hydroxide |
| CNA2006800451921A Pending CN101360782A (en) | 2005-12-06 | 2006-12-01 | Nanocomposite material comprising rubber and modified layered double hydroxide, process for its preparation and use thereof |
| CN2006800452623A Expired - Fee Related CN101321691B (en) | 2005-12-06 | 2006-12-01 | Clay comprising charge-balancing organic ions and nanocomposite materials comprising the same |
| CNA2006800453838A Pending CN101321697A (en) | 2005-12-06 | 2006-12-04 | Process for preparing organically modified layered double hydroxide |
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| CNA2006800451921A Pending CN101360782A (en) | 2005-12-06 | 2006-12-01 | Nanocomposite material comprising rubber and modified layered double hydroxide, process for its preparation and use thereof |
| CN2006800452623A Expired - Fee Related CN101321691B (en) | 2005-12-06 | 2006-12-01 | Clay comprising charge-balancing organic ions and nanocomposite materials comprising the same |
| CNA2006800453838A Pending CN101321697A (en) | 2005-12-06 | 2006-12-04 | Process for preparing organically modified layered double hydroxide |
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| CN (4) | CN101321692B (en) |
| AT (1) | ATE556031T1 (en) |
| BR (1) | BRPI0619473A2 (en) |
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| TWI383849B (en) * | 2008-12-31 | 2013-02-01 | Ind Tech Res Inst | Nano-metal solution, nano-metal complex grains and manufacturing method of conductive wire |
| CN102030943B (en) * | 2009-09-25 | 2012-07-18 | 中国石油化工股份有限公司 | Polypropylene composition and preparation method thereof |
| CN102030944B (en) * | 2009-09-25 | 2012-07-18 | 中国石油化工股份有限公司 | Scratch-resistant polypropylene composition and preparation method thereof |
| KR101130282B1 (en) * | 2009-10-26 | 2012-03-26 | 이화여자대학교 산학협력단 | Sepiocite Compound derived from Layered Double Hydroxide and Method for Preparing the Same |
| CN102009959A (en) * | 2010-09-10 | 2011-04-13 | 北京理工大学 | Preparation method of organic acid anion intercalation hydrotalcite |
| US9410031B2 (en) * | 2011-06-28 | 2016-08-09 | Flow Polymers, Llc | Organic functionalization of layered double hydroxides |
| WO2013173486A1 (en) * | 2012-05-15 | 2013-11-21 | Bridgestone Corporation | Halogenated diene rubber for tires |
| ITUD20130030A1 (en) * | 2013-03-01 | 2014-09-02 | Sumeet Kumar | HYBRID COMPOSITE NANOMATERIALS |
| CN103359792B (en) * | 2013-07-22 | 2015-01-14 | 中国科学院青海盐湖研究所 | MgFe binary hydrotalcite-like compound with high iron content and preparation method thereof |
| EP2933300A1 (en) * | 2014-04-16 | 2015-10-21 | BASF Coatings GmbH | Composition based on layered hydroxides and polyesters, method for preparing the composition and its use |
| CN104192810B (en) * | 2014-08-15 | 2015-10-28 | 浙江大学 | A kind of preparation method of layered double-hydroxide of large interlamellar spacing |
| JP6739435B2 (en) * | 2015-01-06 | 2020-08-12 | エスシージー ケミカルズ カンパニー，リミテッド | SiO2-layered double hydroxide microspheres and method for making the same |
| GB201502832D0 (en) * | 2015-02-19 | 2015-04-08 | Scg Chemicals Co Ltd And Scg Cement Co Ltd | Process for preparing small size layered double hydroxide particles |
| PL3390323T3 (en) * | 2015-12-18 | 2024-02-26 | Saint-Gobain Placo | Gypsum product composition, gypsum products, and a method for using a compound in gypsum board |
| CN110191926A (en) * | 2016-11-15 | 2019-08-30 | Scg化学有限公司 | The modified layered double-hydroxide in surface |
| GB201703558D0 (en) * | 2017-03-06 | 2017-04-19 | Univ Oxford Innovation Ltd | catalysts |
| US10745606B2 (en) * | 2017-08-15 | 2020-08-18 | Saudi Arabian Oil Company | Oil-based drilling fluid compositions which include layered double hydroxides as rheology modifiers |
| CN108948749A (en) * | 2018-07-06 | 2018-12-07 | 佛山市高明区爪和新材料科技有限公司 | A kind of bullet O-shaped rubber seal and preparation method thereof |
| CN110641118B (en) * | 2019-10-17 | 2021-07-27 | 厦门长塑实业有限公司 | High-barrier scratch-resistant biaxially oriented polyamide film and preparation method thereof |
| CN110639366B (en) * | 2019-10-26 | 2021-06-18 | 北京工业大学 | Method for preparing Fe-cage intercalated layered double hydroxide nanofiltration membrane |
| CN113493225B (en) * | 2021-08-11 | 2023-11-10 | 洛阳理工学院 | Preparation method and application of Co/Fe layered double hydroxide nanosheets |
| CN116162304A (en) * | 2023-03-02 | 2023-05-26 | 江苏馨德高分子材料股份有限公司 | Polyethylene sheath material prepared from modified montmorillonite and preparation method thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101360782A (en) | 2009-02-04 |
| BRPI0619473A2 (en) | 2011-10-04 |
| TWI398405B (en) | 2013-06-11 |
| CN101321691B (en) | 2012-07-11 |
| TWI381991B (en) | 2013-01-11 |
| ATE556031T1 (en) | 2012-05-15 |
| TW200734387A (en) | 2007-09-16 |
| CN101321692A (en) | 2008-12-10 |
| TW200736161A (en) | 2007-10-01 |
| CN101321697A (en) | 2008-12-10 |
| TW200734269A (en) | 2007-09-16 |
| TW200734275A (en) | 2007-09-16 |
| ES2385672T3 (en) | 2012-07-30 |
| CN101321691A (en) | 2008-12-10 |
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