CN101321691B - Clay comprising charge-balancing organic ions and nanocomposite materials comprising the same - Google Patents
Clay comprising charge-balancing organic ions and nanocomposite materials comprising the same Download PDFInfo
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- CN101321691B CN101321691B CN2006800452623A CN200680045262A CN101321691B CN 101321691 B CN101321691 B CN 101321691B CN 2006800452623 A CN2006800452623 A CN 2006800452623A CN 200680045262 A CN200680045262 A CN 200680045262A CN 101321691 B CN101321691 B CN 101321691B
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Abstract
The invention relates to a layered double hydroxide having a distance between the individual layers of the layered double hydroxide of above 1.5 nm and comprising 2 or more charge-balancing organic anions having 8 or more carbon atoms, wherein at least 2 of the organic anions have a different number of carbon atoms, and wherein less than 10% of the total of charge-balancing anions are charge-balancing organic anions having 2 or more anionic groups.
Description
The present invention relates to comprise the layered double-hydroxide and uses thereof of the organic anion of two kinds or more kinds of balancing charges.The invention further relates to nano composite material that comprises these layered double-hydroxides and uses thereof.
Layered double-hydroxide (LDH) with organic anion of two kinds or more kinds of balancing charges is known in this area.For example, US 2003/0114699 discloses the mixture that the comprises three kinds of organic anions anionic layered double-hydroxide as balancing charge.Specifically described the hydrotalcite-like anionic clay that contains Triple Pressed Stearic Acid, vinylformic acid and acetate mixture, and the LDH that contains Triple Pressed Stearic Acid, acetate and caproic acid mixture.
WO 2004/019137 has described the for example purposes in toner resin of modified layered double hydroxide.The LDH of these modifications is described as comprising the organic anion of the balancing charge with at least two kinds of anionic groups.The instance of this organic anion is the dicarboxylate of capric acid.WO2004/019137 further discloses has sebacic acid and the stearic mixture anionic LDH as balancing charge.These modifications LDH that notices particle form is as charge control agent.The existence of dicarboxylate causes clay gall to be column ground together, make peel off or delamination very difficulty even maybe.
The purpose of this invention is to provide the modified layered double-hydroxide, it can more be applicable to nano composite material, and the nano composite material that comprises these modified layered double-hydroxides is provided.
The layered double-hydroxide that this purpose surpasses 1.5nm through the distance between the single layer of layered double-hydroxide and comprises the organic anion of 2 kinds or more kinds of balancing charges with 8 or more a plurality of carbon atoms is realized; Wherein at least 2 kinds of organic anions have the carbon atom of different numbers, and are the organic anion with balancing charge of two or more anionic groups less than the negatively charged ion of all balancing charges of 10% wherein.
Compare with comprising organic anionic conventional LDH, layered double-hydroxide of the present invention can more easily be peeled off in polymeric matrix and/or delamination usually, therefore is specially adapted to nano composite material.Therefore, modification LDH is easier in polymeric matrix, process, and this causes more substantial modification LDH to peel off and/or delamination again.The method that these LDH can further make these nano composite materials of preparation is Energy Efficient and more cheap more.Another advantage of these modifications LDH is that the mixing of organic anion of balancing charge is usually more compatible and must be more compatible with polymeric matrix through the combined adjustable of appropriate selection organic anion.
In the application's context, term " organic anion of balancing charge " is meant the insufficient organic ion of compensated crystal LDH electrostatic.Because clay has laminate structure usually, the organic ion of balancing charge can be between the layer of the clay seam of piling up, on the edge or on the outside surface.This organic ion between the stacked clay layer is called the intercalation ion.
This stacked clay or organic clay also can be for example delamination or peel off in polymeric matrix.In the application's context, term " delamination " be defined as through make caly structure at least the part delamination reduce the average accumulation degree of clay particle, produce unit volume thus and contain the significantly material of more single clay gall.Term " is peeled off " and is defined as complete delamination, promptly perpendicular to the disappearance of periodicity on the direction of clay gall, causes individual layer random dispersion in medium, causes not keeping the accumulation order thus.
Be also referred to as the swelling of clay intercalated clay or available X-ray diffraction (XRD) observation of expanding, because basal reflex, i.e. the clear interlamellar spacing of the location tables of d (001) reflection, this distance increases with intercalation.
The reduction of average accumulations degree can be with the broadening of XRD reflection, and until disappearance, or observes through the asymmetry increase of basal reflex (001).
Fully delamination, the sign of promptly peeling off still has analytical challenge, but usually can through non--(hk0) reflect from original clay completely dissolve to infer.
The order of layer can further be observed with transmission electron microscopy (TEM) with extent of delamination therefore.
The LDH that comprises the organic anion of balancing charge can have the laminate structure corresponding to following general formula:
M wherein
2+Be divalent-metal ion such as 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 such as Al
3+, Cr
3+, Fe
3+, Co
3+, Mn
3+, Ni
3+, Ce
3+And Ga
3+, m and n have makes the value of m/n=1-10, and b has the value in the scope of 0-10.X is 2 kinds or more kinds of organic anion and optional following any other organic anion or the mixture of inorganic anion of comprising with balancing charge of 8 or more a plurality of carbon atoms: hydroxide radical, carbonate, bicarbonate radical, nitrate radical, cl ions, bromide anion, sulfonate radical, sulfate radical, bisulfate ion, alum acid group, wolframate radical, borate, phosphate radical.As far as this specification sheets, carbonate and bicarbonate radical are defined as inorganic in nature.
LDH of the present invention comprises hydrotalcite and hydrotalcite-like anionic LDH.The instance of this type LDH is hydroxyl pyrope, manasseite (manasseite), pyroaurite, sjogrenite
stichtite, barbierite (barberonite), takovite, reevesite and water carbon manganese magnesite.In one embodiment of the invention, layered double-hydroxide has the laminate structure corresponding to following general formula:
Wherein m and n have the m/n=1-10 of making, preferred 1-6, and more preferably 2-4 most preferably approaches 3 value; And the value of b is 0-10, and 2-6 usually is about 4 usually.X is the as above ion of defined balancing charge.Preferred m/n should have the value of 2-4, more especially preferably approaches 3 value.
LDH can have any crystalline form known in the art, as describing by Cavani etc. (CatalysisToday, 11 (1991), the 173-301 page or leaf) or by (Clays and Clay Minerals, (1993), the 41st (5) volume, 558-564 pages or leaves) such as Bookin, like 3H
1, 3H
2, 3R
1Or 3R
2Pile up.
Distance among the LDH between the single clay seam is usually greater than only containing carbonate as the distance between the anionic LDH layer of balancing charge.Preferably interlamellar spacing is 1.5nm at least in LDH of the present invention, more preferably 1.8nm at least, most preferably 2nm at least.Distance between the single layer can use X-ray diffraction to measure as stated.
LDH of the present invention comprises 2 kinds or more kinds of organic anion with balancing charge of 8 or more a plurality of carbon atoms.At least 2 kinds of these organic anions have the carbon atom of different numbers.That the instance that this type has an organic anion of at least 8 carbon atoms comprises is single-, two-or polycarboxylic acid root, sulfonate radical, phosphonate radical, nitrate radical and sulfate radical.Preferred organic anion comprises at least 10 carbon atoms, preferred 10-40 carbon atom, most preferably 12-30 carbon atom.Imagination is used 2 kinds or more kinds of organic anion, and wherein at least a have at least 8 carbon atoms, and gained LDH has the interlamellar spacing of 1.5nm at least; A kind of in other organic anion so can have and be less than 8 carbon atoms.
Further the organic anion of imagination balancing charge comprises one or more functional groups: propenoate; Methacrylic ester; Hydroxyl; Muriate; Amine; Epoxy group(ing); Thiol group; Vinyl; Disulphide (disulfide); Polysulfide (polysulfide); Carbamate; Ammonium; Sulfonium;
; Phospho acid; Isocyanic ester; Sulfydryl; Hydroxy phenyl; Hydrogenate; Acetoxyl group and acid anhydrides.If the LDH that this type is organically-modified is used for polymeric matrix, then these functional groups can with interpolymer interaction or reaction.
Notice that the organic anion less than all balancing charges of 10% is the organic anion with two or more anionic groups.In the application's context, term " anionic group " is meant the group with anionic charge.This anionoid examples of groups is carboxylate radical, sulphonic acid anhydride, phosphonate radical, nitrate radical and sulfate radical.More not preferred these organic anions have 2 or more a plurality of anionic group, because they can interconnect the successive layer usually, they can not be peeled off or delamination, and therefore are not suitable for nano composite material.For this reason, this type should keep below 10 moles of % of the organic anion total amount of balancing charge as the amount of the anionic organic anion of balancing charge, preferably is lower than 5mol%, more preferably less than 2mol%.In one embodiment of the invention, there is not organic anion with 2 or more a plurality of anionic groups.
The instance that is applicable to the organic anion of LDH of the present invention is the monocarboxylic acid root like the negatively charged ion that is derived from lipid acid, the negatively charged ion that is derived from naphthenic acid with based on the rosiny ion.
LDH of the present invention can comprise two kinds or more kinds of organic anion with 8-22 carbon atom that is derived from saturated or unsaturated fatty acids.Modification LDH can comprise the organic anion (mixture that promptly comprises the various carboxylic acids of pentamethylene ring) that is derived from naphthenic acid.Also can comprise based on rosiny acid and the anionic combination that is derived from saturated or unsaturated fatty acids.
The anionic instance with 8-22 carbon atom that is derived from lipid acid comprises the organic anion that is derived from 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.
Based on rosiny acid or rosin be derived from natural source, cheapness is easy to obtain and compares with synthetic organic anion.The representative instance of natural sources of rosin is gum resin, wood rosin and starex.Rosin is generally the mixture of different isomerization body of the monobasic three ring sylvic acids (monocarboxylictricyclic rosin acid) of the wide region that often contains 20 carbon atoms of having an appointment.The key distinction of the tricyclic structure of various sylvic acids is the position of two keys.Rosin is generally the mixture of the material that comprises levopimaric acid, neoabietic acid, palustric acid, abietic acid, dehydroabietic acid, seco dehydroabietic acid, tetrahydroabietic acid, dihydroabietic acid, pimaric acid and isopimaric acid.The rosin that is derived from natural source also comprises through polymerization, isomery, disproportionation, hydrogenation and the rosin of remarkable modification, i.e. rosin mixture with vinylformic acid, acid anhydrides and propenoate Diels-Alder reaction.The products known as modified rosin that obtains through these methods.Natural rosin also can be through any method known in the art chemical modification, as make carboxyl and MOX, metal hydroxides or reactant salt on the rosin form rosined soap or salt (so-called abietate).These chemical modification rosin are called rosin derivative.
This rosin can modification or chemically changed through introducing organic group, anionic group or cation group.Organic group can be replacement or unsubstituted aliphatic series or the aromatic hydrocarbon with 1-40 carbon atom.Anionic group can be the known any anionic group of those skilled in the art such as carboxylate radical or sulfonate radical.
These other details based on the rosiny material can be from D.F.Zinkel and J.Russell (in Naval Stores (rosin goods), production-chemistry-utilization, 1989; NewYork, II joint, the 9th chapter) and J.B.Class (" Resins; Natural, " the 1st chapter: " Rosinand Modified Rosins, " Kirk-Othmer Encyclopedia of ChemicalTechnology; The online delivery date:, December 4 in 2000) find in.
In another embodiment of the present invention, LDH comprises 3 kinds or more kinds of organic anion with balancing charge of 8 or more a plurality of carbon atoms.Preferred LDH of the present invention comprises 4 kinds or more kinds of organic anion with balancing charge of 8 or more a plurality of carbon atoms.It is many more as the organic anion of the organic anion existence of balancing charge that certificate is thought, modification LDH peels off in polymeric matrix or intercalation more easily.In addition, these modifications LDH polymeric matrix common and more wide region is more compatible.
Imagination can exist to have less than other organic anions of 8 carbon atoms and/or the as above defined inorganic anion negatively charged ion as balancing charge in modification LDH of the present invention except that the organic anion with 8 or more a plurality of carbon atoms.
Usually; In LDH type of the present invention; At least 10% of intercalation total ion concentration is 2 kinds or more kinds of organic anion mixture with 8 or more a plurality of carbon atoms; At least 30% of preferred intercalation total ion concentration, more preferably at least 60%, most preferably at least 90% is 2 kinds or more kinds of organic anion mixture with 8 or more a plurality of carbon atoms.In one embodiment of the invention; The intercalant anion total amount at least 10% for being derived from lipid acid or based on rosiny negatively charged ion or both mixtures; At least 30% of the total ion concentration of preferred balancing charge; More preferably at least 60%, most preferably at least 90% for being derived from lipid acid or based on rosiny negatively charged ion or both mixtures.
LDH of the present invention can prepare with the mode that is similar to the currently known methods for preparing the prior art organic clay.The instance that this type is used for the method for LDH can find at WO 00/09599.
Be applicable to that the method for preparing organic clay of the present invention comprises:
A. use organic ion IX;
B. synthesis of clay in the presence of organic ion;
C. calcined clay, hydration again in the presence of organic ion subsequently;
D. with the carbanion of mineral acid exchange clay, use organic ion IX subsequently,
For other method, with reference to Carlino (Solid State Ionics, 1996,98,73-84 page or leaf).In the document, the method for the switching method of carrying out such as heat or melt reaction method with glycerine has been described.According to heat or melt reaction method, with the mixture of LDH and organic anion under elevated temperature, preferred thorough mixing under the temperature of the melt temperature that is higher than organic anion with high melting temperature.According to the switching method of carrying out with glycerine, with glycerine intermediate swellings LDH, introduce the mixture of organic anion then, carry out intercalation subsequently.Notice that this method also can use the swelling reagent that is different from glycerine such as ethanol, 2-oxyethyl group propyl alcohol, 2-propyl alcohol, butanols, triglycol etc. to carry out.Perhaps, LDH of the present invention can prepare through the negatively charged ion of balancing charge and the melt blending of clay.
LDH of the present invention can be used as coating composition, (printing) ink formulations, tackiness agent tackifier, the compsn based on resin, rubber combination, cleaning formulations, drilling fluid and cement, gypsum preparaton, supatex fabric, fiber, foam, film, orthoplast casting (orthoplastic cast), (preceding-) stupalith, and the miscellaneous composite organic-inorganic material is like the component based on the nano composite material of polymkeric substance.LDH of the present invention can be further used for polyreaction such as solution polymerization, letex polymerization and suspension polymerization.Organic clay also can be used as crystallization auxiliary in semi-crystalline polymer such as Vestolen PP 7052.LDH of the present invention can be further used for wherein can application with the independent function combinations of LDH and organic anion in, as be used for paper technology or cleaned industry.In addition, LDH of the present invention can be used for the sustained release of medicine, agricultural chemicals and/or fertilizer and uses, and the sorbent material that is used as organic cpds such as pollutent, tinting material etc.
The invention further relates to the nano composite material that comprises polymeric matrix and LDH of the present invention.Use the LDH of modification of the present invention, can in the polymeric matrix of wide region more, obtain peeling off and/or delamination of higher degree, and the amount of the modification LDH of micron-scale normally low or even be zero.This makes and can in nano composite material, use the low modification LDH that measures.Therefore the nano composite material that has than low density and good mechanical properties can be provided.In nano composite material, peel off fully and/or the LDH of delamination can make material to visible transparent, therefore make it be applicable to optical applications.
Term " nano composite material " is meant that wherein at least a component comprises the matrix material that one dimension at least is positioned at the inorganic phase of 0.1-100 nanometer range.
That be specially adapted to nano composite material of the present invention is the LDH of mixture that comprises the organic anion of following balancing charge, and the organic anion chemically changed of at least a balancing charge must perhaps be reactive to polymeric matrix mutually with polymeric matrix in this mixture.This causes interactional improvement between LDH and the polymeric matrix, causes improved machinery and/or viscoelastic property.More compatible organic anion can comprise replacement or unsubstituted aliphatic series or the aromatic hydrocarbon with 1-40 carbon atom.Perhaps or in addition, at least a organic anion can comprise and is selected from following reactive group: propenoate, methacrylic ester, hydroxyl, muriate, amine, epoxy group(ing), thiol group, vinyl, disulphide (disulfide), polysulfide (polysulfide), carbamate, ammonium, sulfonic acid,-sulfinic acid, sulfonium,
, phospho acid, isocyanic ester, sulfydryl, hydroxy phenyl, hydrogenate, acetoxyl group and acid anhydrides.
Polymkeric substance applicable to nano composite material of the present invention can be any polymeric matrix known in the art.In this manual, term " polymer " " be meant and have at least two structural units organic substance of (being monomer) therefore comprise oligopolymer, multipolymer and fluoropolymer resin.The polymkeric substance that is applicable to polymeric matrix is addition polymer and polycondensate.Polymkeric substance may further be homopolymer or multipolymer.
The polymerization degree of preferred polymers matrix is at least 20, more preferably at least 50.Thus, in order to define the polymerization degree, with reference to P.J.Flory, Principles of Polymer Chemistry, New York, 1953.
The instance of suitable polymers is polyolefine such as Vilaterm or Vestolen PP 7052, vinyl polymer such as PS, polymethylmethacrylate, SE, polyvinylidene dichloride or PVDF, saturated polyester such as polyethyleneterephthalate, POLYACTIC ACID or gather (6-caprolactone), unsaturated polyester resin, acrylate resin; Methacrylate resin, polyimide, epoxy resin, resol; Urea-formaldehyde resin, melamine-formaldehyde resin, urethane, polycarbonate; Polyaryl ether, polysulfones, polythioether, polymeric amide; Polyetherimide, polyether ester, polyetherketone, polyether ester ketone; ZGK 5, urethane, polyepoxide, and the blend of two kinds or more kinds of polymkeric substance.Preferred polyolefine, vinyl polymer, polyester, polycarbonate, polymeric amide, urethane or the polyepoxide of using.
Organic clay of the present invention is specially adapted to thermoplastic polymer such as Vilaterm, Vestolen PP 7052, PS; And acetal (being total to) polymkeric substance such as polyoxymethylene (POM); And rubber such as tree elastomer (NR), styrene-butadiene rubber(SBR) (SBR), TR 301 (IR), polyhutadiene (BR), polybutylenes (IIR), halogenation polyisobutene, paracril (NBR), hydrogenated nitrile-butadiene rubber (HNBR), styrene-isoprene-phenylethene (SIS) and similar styrenic block copolymer; Hydrin rubber (CO, ECO, GPO), Zylox (Q), X 050 (CR), ethylene-propylene rubber(EPR) (EPM), ethylene-propylene-elastoprene (EPDM), thiorubber (T), viton (FKM), ethylene-vinyl acetate rubber (EVA), polyacrylic rubber (ACM), polynorbornene (PNR), urethane (AU/EU), and polyester/ether thermoplastic elastomer.
Particularly preferably be the polymkeric substance or the multipolymer that can obtain through at least a ethylenically unsaturated monomer of polymerization.The instance of this base polymer is polyolefine and modified polyolefin, and they are known by those of ordinary skill in the art.Polyolefine or modified polyolefin can be homopolymer or multipolymer.This type (modification) polyolefinic suitable example is Vilaterm, Vestolen PP 7052, polybutylenes, PS, SE, polyvinylidene dichloride, and ethylene-propylene rubber(EPR), propene-1-butene copolymer, ethylene-vinyl chloride copolymer, vinyl-vinyl acetate copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), AAS acrylonitrile acryloid styrene (AAS), MBS (MBS), chlorinatedpolyethylene, Chlorinated Polypropylene III, ethylene-acrylate copolymer, VCP and composition thereof.Even preferred polymkeric substance is Vilaterm, Vestolen PP 7052, PS and SE.
Poly specific examples is high density polyethylene(HDPE), new LDPE (film grade), straight-chain low density polyethylene, ultra-low density polyethylene and ultrahigh molecular weight polyethylene(UHMWPE).Instance based on the multipolymer of ethene is vinyl-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA) and ethylene-acrylic acid copolymer (EAA).
Most preferred polymkeric substance is a Vestolen PP 7052.Any Vestolen PP 7052 known in the art is applicable to the present invention.Polyacrylic instance is for to deliver the date on the net: the R.B.Lieberman on December 4th, 2000, Kirk-Othmer Encyclopedia of Chemical Technology, " polypropylene ", the 1st chapter: " Properties,, in provide.The Vestolen PP 7052 of certain kinds of the present invention is to be formed by so-called TPO (TPO), and it comprises Vestolen PP 7052 and the EPR rubber blend or the reagent trade mark (reactorgrade).
Nano composite material of the present invention can further comprise the additive that is usually used in this area.The instance of this type additive is pigment, dyestuff, UV stablizer, thermo-stabilizer, inhibitor, filler (like talcum, chalk, lime, hydroxylapatite, silica, carbon black, spun glass, natural and synthetic polymeric fibers and other inorganic materials), fire retardant, nucleator, impact modifier, softening agent, rheology modifier, linking agent, coupling agent and air release agent.
Additive that these are optional and corresponding amount thereof can be selected as required.
The amount of LDH is preferably 0.01-75 weight % based on the gross weight of mixture in nano composite material, more preferably 0.05-50 weight %, even more preferably 0.1-30 weight %.
10 weight % or lower, preferred 1-10 weight %, more preferably the LDH of 1-5 weight % amount is to the nano composite material of preparation based on polymkeric substance, and it is especially favourable promptly to contain delamination-contain the compsn of polymkeric substance until the present invention of the organically-modified LDH that peels off.
10-70 weight %, more preferably the LDH of 10-50 weight % amount promptly for example is used for the high density additive pre-composition particularly advantageous of compounding of polymers to preparing so-called masterbatch.Although clay is fully delamination and/or peel off usually in this masterbatch, need, further delamination and/or peel off can be in follow-up phase is realizing masterbatch and another polymer blending when obtaining real nano composite material based on polymkeric substance.
Nano composite material of the present invention can be according to the known any method preparation of those skilled in the art.Those of skill in the art can be through using for example melt blended technology with polymeric matrix and organic clay thorough mixing of the present invention.This method is preferred, because it is simple, cost effective and can be easy to be applied to existing apparatus.Also imagine in the presence of polymeric matrix, or in the presence of monomer and/or the oligopolymer and before monomer and/or oligopolymer polymerization form polymeric matrix, among or prepare clay of the present invention afterwards.Other details of preparation and processing polypropylene can be delivered the date on the net: the R.B.Lieberman on December 4th, 2000; Kirk-Othmer Encyclopedia of Chemical Technology; " polypropylene ", the 2nd chapter: " Manufacture " and the 3rd chapter: find in " Processing ".
Nano composite material of the present invention can be used for wherein using usually in any application of these matrix materials.Nano composite material is applicable in carpet, trolley part, container closure, lunch box, closure, medical treatment device, household supplies, food product containers, dishwasher, outdoor furniture, blow molded bottle, Disposable, nonwoven fabric, cable and line and the packing.Polyacrylic other details can be delivered the date on the net: the R.B.Lieberman on December 4th, 2000, Kirk-Othmer Encyclopedia ofChemical Technology " polypropylene ", the 5th chapter: " Uses "; And be to find in " polypropylene:Textile; Rigid Packaging, Consumer, Film; Automotive, Electrical/Electronics and HomeAppliances " at the pph 022PPe of Basell 10/01 title.
The nano composite material that comprises rubber applicable to the tire manufacturing as being used for green tire, truck tyre, tractor tire, engineering tyre and aircraft tire, winter tyre (winter tyre); Be used for latex products; It comprises gloves, condom, balloon, conduit, latex thread, foam, carpet backing and gluing coconut fiber and mane, footwear; Be used for civil engineering work product such as bridge pad, rubber-metal lamination bearing, band and flexible pipe; Be used for non-tire automotive applications; It comprises hood, rubber support, strip of paper used for sealing, packing ring, washer and automobile rear, is used for line and cable and is used for the seal of tube, Medical bottle stopper, cylinder, small-sized solid tyre, used for cosmetic utensil and commercial applications, rubber sphere and pipeline, milk inflation (milking inflation) and other application based on agricultural.
If rubber is Zylox and modified layered double hydroxide is according to of the present invention; Then these nano composite materials are applicable to coating products; It comprises pressure sensitive adhesive, plastics dura mater (plastichardcoat) and paper anti-stick coating; Be used for fibre finish and use, it comprises fabric and hair nursing application, sealing agent, tackiness agent, encapsulation agent and solar battery cell.
The present invention further specifies in following embodiment.
Accompanying drawing is described
Fig. 1 has shown the TEM photo of the SBR rubber nano composite material of Comparative Examples 4.
Fig. 2 is the TEM photo of the SBR rubber nano composite material of embodiment 5.
Embodiment
Directly use commercially available lipid acid.
PH05 (palmitinic acid and stearic blend) is provided by Oleochemicals GmbH (company of Akzo Nobel Chemicals).
In addition, use the rosin of stabilization.The rosin of stabilization is through with the Chinese gum rosin fusion and be heated to 235 ℃ and internal pair production.In melting process, adding based on rosin is
-2 (available from Arkema Inc.) of 3.5 weight %.Molten rosin was stirred 15 hours down at 235 ℃, then rosin is cooled off subsequent use.
Embodiment 1
With 68.2 the gram Natural manganese dioxide (
40, available from Martin Marietta MagnesiaSpecialties LLC) and 43.6 gram white lakes (Alumill F505) in 840 gram softening waters, mix and be ground to mean particle size (d
50) be 2.5 μ m.Slurry is infeeded in the autoclave of the oil heating of being furnished with high speed agitator and be heated to 80 ℃.Then, the suspension-s that in 15 fens clockwise autoclaves, adds 132 gram
PH05 and rosiny 50/50 weight ratio of the stabilization that as above prepares.Before reinforced, sour suspension-s is heated to 80C.After adding acid, that autoclave is closed and be heated to 170 ℃ and under this temperature, kept 1 hour.Then autoclave is cooled to about 40 ℃, and shifts out the gained slurry.Then with slurry under 2000rpm centrifugal about 10 minutes.Decanting liq, and with solid in baking oven in vacuum and 80 ℃ of following dried overnight.
With X-ray diffraction analysis package fatty acids and based on rosiny ionic gained hydrotalcite-like clay to measure interlamellar spacing or d-spacing.As above the XRD spectra of the hydrotalcite-like clay of preparation shows small non--(hk0) reflection that relates to hydrotalcite, and this has shown the intercalation of anionic clay.Characteristic d (001) value that this intercalation shows
, this
or
d-spacing more than the pure water talc clay is big.
Comparative Examples 2
With 300 the gram Natural manganese dioxide (
40, available from Martin Marietta MagnesiaSpecialties LLC) and 230 gram white lakes (Alumill F505) in 648 gram softening waters, mix and be ground to mean particle size (d
50) be 2.5 μ m.Slurry is infeeded in the autoclave of the oil heating of being furnished with high speed agitator and be heated to 120 ℃.Then, added 670 gram Triple Pressed Stearic Acid (available from Acros) in the clockwise autoclave through 30 minutes.Before reinforced, lipid acid is heated to 120 ℃.After adding acid, autoclave is heated to 170 ℃ and under this temperature, kept 1 hour.Then autoclave is cooled to about 40 ℃, and shifts out the gained slurry.Use spun glass filter slurry and with the gained solid in baking oven in vacuum and 80 ℃ of following dried overnight.
With the gained hydrotalcite-like clay of X-ray diffraction analysis package fatty acids to measure interlamellar spacing or d-spacing.As above the XRD spectra of the hydrotalcite-like clay of preparation shows small non--(hk0) reflection that relates to hydrotalcite, and this has shown the intercalation of anionic clay.Characteristic d (001) value that this intercalation shows
.
Embodiment 3
Directly use commercially available lipid acid.
PH05 (palmitinic acid and stearic blend) is provided by Oleochemicals GmbH (company of Akzo Nobel Chemicals).
With 50 the gram Natural manganese dioxide (
40, available from Martin Marietta MagnesiaSpecialties LLC) and 39 gram white lakes (Alumill F505) in 648 gram softening waters, mix and be ground to mean particle size (d
50) be 2.5 μ m.Slurry is infeeded in the autoclave of the oil heating of being furnished with high speed agitator and be heated to 120 ℃.Then, added 102 gram
PH05 in the clockwise autoclave through 30 minutes.Before reinforced, fatty acid blend is heated to 120 ℃.After adding acid, autoclave is heated to 170 ℃ and under this temperature, kept 1 hour.Then autoclave is cooled to about 40 ℃, and shifts out the gained slurry.Then with slurry under 2000rpm centrifugal about 10 minutes.Decanting liq, and with solid in baking oven in vacuum and 80 ℃ of following dried overnight.
With the gained hydrotalcite-like clay of X-ray diffraction analysis package fatty acids to measure interlamellar spacing or d-spacing.As above the XRD spectra of the hydrotalcite-like clay of preparation shows small non--(hk0) reflection that relates to hydrotalcite, and this has shown the intercalation of anionic clay.Characteristic d (001) value that this intercalation shows
.
Comparative Examples 4 and embodiment 5
Use Hosokawa Alpine50 ZPS circoplex multistep processing grinding machine that the modified layered double-hydroxide of embodiment 2 is ground separately.Measure according to DIN 13320, the d50 value of gained powder is that 1.9 μ m and d90 value are 5.7 μ m.
The powdered modified LDH that comprises 50 weight % Comparative Examples 2 and the masterbatch of 50 weight %
1502 (SBR rubber is available from Polimeri) have been prepared.
1502 infeeded in the open type dual-roller grinding machine (Agila), added powdered modified LDH then through 30 minutes.Two roller mills are operated under 50-70 ℃ temperature and frictional coefficient is 1.2.
On the open type dual-roller grinding machine of operating under the condition same as described above,, in rubber, obtain the modification LDH ultimate density of 10phr with identical rubber precursor dilution gained masterbatch.In second step; The sample that makes diluted compounds in the internal mixer (
90 is furnished with the 60CC mixing section
600 that contains the roller rotor) 60 ℃ with 50rpm under peeled off 10 minutes.
In two roller mills; Then will about 50g gained sample and 0.52phr dicumyl peroxide (
BC-ff is available from Akzo Nobel) mixing.Two roller mills under 50-70 ℃, operate and frictional coefficient is 1.2.With the mixture that so obtains 170 ℃ with 400kN under final mold pressing became the sheet that thickness is 2mm in 15 minutes, to obtain SBR rubber nano composite material (nano composite material of Comparative Examples 4).
Use the tem study nano composite material.Gained TEM photo is shown in Fig. 1.
Use program same as described above to grind the modification LDH of embodiment 3.The gained powder has the d50 value of 4.0 μ m and the d90 value of 10.5 μ m.
Preparation comprises the powdered modified LDH of 50 weight % embodiment 3 and second masterbatch of 50 weight %
1502 in the same manner as described above.
The TEM photo of this nano composite material (nano composite material of embodiment 5) is shown in Fig. 2.
The TEM photo of Fig. 1 and Fig. 2 has shown the distribution of clay in the SBR rubber matrix.Obviously, Fig. 1 has shown the big clay particle in rubber matrix, and these big particles do not exist in Fig. 2.In addition, the distribution of the clay gall among Fig. 2 is better than observed distribution among Fig. 1.Generally speaking, compare with the LDH of Comparative Examples 2, the nano composite material that comprises LDH of the present invention shows that clay is easier to delamination/peel off, and in the SBT rubber matrix, shows improved clay distribution.
Claims (15)
1. the distance between the single layer of a layered double-hydroxide surpasses 1.5nm and comprises the layered double-hydroxide of the organic anion of 2 kinds or more kinds of balancing charges with 8 or more a plurality of carbon atoms; Wherein at least 2 kinds of organic anions have the carbon atom of different numbers, and wherein do not have the organic anion of the balancing charge with two or more anionic groups.
2. according to the layered double-hydroxide of claim 1, it comprises 3 kinds or more kinds of organic anion with balancing charge of 8 or more a plurality of carbon atoms.
3. according to the layered double-hydroxide of claim 1, it comprises 4 kinds or more kinds of organic anion with balancing charge of 8 or more a plurality of carbon atoms.
4. according to each layered double-hydroxide among the claim 1-3, the organic anion that wherein has 8 or more a plurality of carbon atoms accounts for the ionic 50% of all balancing charges at least.
5. nano composite material that in polymeric matrix, comprises according to each layered double-hydroxide among the claim 1-4.
6. according to the nano composite material of claim 5, wherein said polymeric matrix comprises the polymkeric substance that obtains through at least a ethylenically unsaturated monomer of polymerization.
7. according to the nano composite material of claim 5, wherein said polymeric matrix comprises the multipolymer that obtains through at least a ethylenically unsaturated monomer of polymerization.
8. according to the nano composite material of claim 5, wherein said polymkeric substance is a rubber.
9. according to each nano composite material among the claim 5-8, its gross weight based on this nano composite material comprises 1-10 weight % layered double-hydroxide.
10. masterbatch, its gross weight based on matrix material comprise 10-70 weight % according to each layered double-hydroxide among the claim 1-4, and 30-90 weight % polymkeric substance.
11. according to each layered double-hydroxide among the claim 1-4 at coating composition, ink formulations, tackiness agent tackifier, compsn, cleaning formulations, drilling fluid, cement, gypsum preparaton, supatex fabric, fiber, foam, film, orthoplast casting, stupalith, polyreaction, paper, washing composition based on resin; The sustained release of medicine, agricultural chemicals and/or fertilizer is used, or the purposes of the sorbent material of organic cpds.
12. according to each the purposes of layered double-hydroxide in rubber combination among the claim 1-4.
13. according to each the purposes of nano composite material in carpet, trolley part, medical treatment device, household supplies, dishwasher, outdoor furniture, blow molded bottle, Disposable, nonwoven fabric, cable or wire and packing among the claim 5-9.
14. according to each the purposes of nano composite material in food product containers among the claim 5-9.
15. according to the purposes of claim 14, wherein said food product containers is a lunch box.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
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| EP05111752.1 | 2005-12-06 | ||
| EP05111752 | 2005-12-06 | ||
| EP05112820 | 2005-12-22 | ||
| EP05112820.5 | 2005-12-22 | ||
| US75958306P | 2006-01-18 | 2006-01-18 | |
| US60/759,583 | 2006-01-18 | ||
| PCT/EP2006/069207 WO2007065861A1 (en) | 2005-12-06 | 2006-12-01 | Clay comprising charge-balancing organic ions and nanocomposite materials comprising the same |
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| Publication Number | Publication Date |
|---|---|
| CN101321691A CN101321691A (en) | 2008-12-10 |
| CN101321691B true CN101321691B (en) | 2012-07-11 |
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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 |
| CN2006800457383A Expired - Fee Related CN101321692B (en) | 2005-12-06 | 2006-12-01 | Process for preparing organically modified layered double hydroxide |
| 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 |
| CN2006800457383A Expired - Fee Related CN101321692B (en) | 2005-12-06 | 2006-12-01 | Process for preparing organically modified layered double hydroxide |
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| CNA2006800453838A Pending CN101321697A (en) | 2005-12-06 | 2006-12-04 | Process for preparing organically modified layered double hydroxide |
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| CN (4) | CN101360782A (en) |
| AT (1) | ATE556031T1 (en) |
| BR (1) | BRPI0619473A2 (en) |
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| TW (4) | TWI381991B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3390323B1 (en) * | 2015-12-18 | 2023-11-15 | Saint-Gobain Placo | Gypsum product composition, gypsum products, and a method for using a compound in gypsum board |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| US9657157B2 (en) * | 2012-05-15 | 2017-05-23 | 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 |
| DK3245258T3 (en) * | 2015-01-06 | 2019-10-07 | Scg Chemicals Co Ltd | SiO2 LAYERED DOUBLE HYDROXIDE MICROBULS AND METHODS OF PRODUCING IT |
| 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 |
| KR20190085533A (en) | 2016-11-15 | 2019-07-18 | 에스씨지 케미컬스 컴퍼니, 리미티드. | The surface-modified layered double hydroxide |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030114699A1 (en) * | 2001-08-23 | 2003-06-19 | Aristech Chemical Corporation | Novel hydrotalcites, syntheses, and uses |
| CN1675594A (en) * | 2002-08-03 | 2005-09-28 | 科莱恩有限公司 | Use of salts of layered double hydroxides as charge control agents |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5518704A (en) * | 1993-07-06 | 1996-05-21 | Aristech Chemical Corporation | Nickel and cobalt containing hydrotalcite-like materials having a sheet-like morphology and process for production thereof |
| DE19836580A1 (en) * | 1998-08-12 | 2000-02-17 | Sued Chemie Ag | A compound material with a polymer matrix and a double layer hydroxide with anionic compounds between the layers useful for nano-composite-fillers in polymer matrixes avoids the use of expensive quaternary ammonium compounds |
| KR20010086374A (en) * | 1999-07-08 | 2001-09-10 | 나카자와 타다히사 | Composite polybasic salt, process for producing the same, and use |
| US6979708B2 (en) * | 2001-08-23 | 2005-12-27 | Sunoco, Inc. (R&M) | Hydrotalcites, syntheses, and uses |
| NO20035745D0 (en) * | 2003-12-19 | 2003-12-19 | Amersham Health As | Process |
| JP4058767B2 (en) * | 2004-11-04 | 2008-03-12 | 船井電機株式会社 | Switching power supply |
-
2006
- 2006-12-01 CN CNA2006800451921A patent/CN101360782A/en active Pending
- 2006-12-01 CN CN2006800457383A patent/CN101321692B/en not_active Expired - Fee Related
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- 2006-12-01 CN CN2006800452623A patent/CN101321691B/en not_active Expired - Fee Related
- 2006-12-01 BR BRPI0619473-7A patent/BRPI0619473A2/en not_active IP Right Cessation
- 2006-12-04 CN CNA2006800453838A patent/CN101321697A/en active Pending
- 2006-12-06 TW TW095145442A patent/TWI381991B/en not_active IP Right Cessation
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030114699A1 (en) * | 2001-08-23 | 2003-06-19 | Aristech Chemical Corporation | Novel hydrotalcites, syntheses, and uses |
| CN1675594A (en) * | 2002-08-03 | 2005-09-28 | 科莱恩有限公司 | Use of salts of layered double hydroxides as charge control agents |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3390323B1 (en) * | 2015-12-18 | 2023-11-15 | Saint-Gobain Placo | Gypsum product composition, gypsum products, and a method for using a compound in gypsum board |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200734387A (en) | 2007-09-16 |
| CN101360782A (en) | 2009-02-04 |
| TWI381991B (en) | 2013-01-11 |
| ES2385672T3 (en) | 2012-07-30 |
| BRPI0619473A2 (en) | 2011-10-04 |
| TWI398405B (en) | 2013-06-11 |
| CN101321692B (en) | 2012-08-22 |
| TW200736161A (en) | 2007-10-01 |
| TW200734269A (en) | 2007-09-16 |
| CN101321692A (en) | 2008-12-10 |
| CN101321697A (en) | 2008-12-10 |
| CN101321691A (en) | 2008-12-10 |
| ATE556031T1 (en) | 2012-05-15 |
| TW200734275A (en) | 2007-09-16 |
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