CN1796465A - Insertion layer of montmorillonite and face finish, and using inserted layer and face finished montmorillonite to prepare polybutadiene / Nano 'Fuximuxi Mujiao' of montmorillonite - Google Patents
Insertion layer of montmorillonite and face finish, and using inserted layer and face finished montmorillonite to prepare polybutadiene / Nano 'Fuximuxi Mujiao' of montmorillonite Download PDFInfo
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- CN1796465A CN1796465A CN 200410102517 CN200410102517A CN1796465A CN 1796465 A CN1796465 A CN 1796465A CN 200410102517 CN200410102517 CN 200410102517 CN 200410102517 A CN200410102517 A CN 200410102517A CN 1796465 A CN1796465 A CN 1796465A
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Abstract
This invention describes a process for interlayer insertion and surface modification of montmorillonite, and preparation of the polybutadiene/montmorillonite nanocomposite from the inserted and surface modified montmorillonite. In the process, a quaternary ammonium salt is used to carry out cation-exchange reaction with the montmorillonite, which is then subjected to surface modification with a coupling agent so that the modified montmorillonite exhibits improved hydrophobicity and can be dissolved in nonpolar solvents such as cyclohexane to form a stable dispersing system. The dispersing system of the modified montmorillonite and cyclohexane, butadiene, an optional polar additive and alkyl lithium are subjected to the classic anion solution polymerization to realize the in situ interlayer insertion polymerization of the butadiene monomer, and the prepared polybutadiene/montmorillonite nanocomposite has improved mechanical properties, heat durability and chemical corrosion resistance as well as a good balance among the over-all properties.
Description
Technical field
The present invention relates to a kind of intercalation of polynite and polyhutadiene/Nano composite material of montmorillonite that surface modification method, the polynite of use after intercalation and finishing prepare the method for polyhutadiene/Nano composite material of montmorillonite and prepare thus.
Background technology
Nano composite polymer-montmorillonoid material (PLSN) is owing to have the unexistent structure of conventional matrix material, form and performances such as more excellent mechanics, calorifics, fire-retardant, obstruct, since the graduate scientist of Toyota Motor in 1987 has prepared the polyamide 6/Nano composite material of montmorillonite with nanostructure, caused people's common concern at once.
But because polynite has high surface energy, in matrix, be easy to reunite, dispersion effect is bad in non-polar solvent, poor with the consistency of polymerizable organic monomer, polymerisable monomer can not interposed layer between and realize in-situ polymerization, therefore must carry out organic modification to polynite, make the polynite surface become hydrophobicity by wetting ability, wherein the selection of organic modification agent is the key of organ-mmt modifying process.
Studies show that strong polar polynite is through could disperseing in non-polar solvent better behind the organic modification, polymerisable monomer could more effectively enter montmorillonite layer, preparation intercal type and even exfoliated nano-composite.In the past few decades, people are doing a large amount of work aspect the organ-mmt modification.Reported a large amount of researchs about organ-mmt modification aspect, wherein organic modification is divided into two kinds of methods: organic cation intercalation modifying and surperficial coupling modification.
At present, mainly concentrate on the quaternary ammonium salts modification for the research of organ-mmt modification among the PLSN, and adopt coupling agent to carry out surperficial coupling modification on a small quantity.In numerous organ-mmt properties-correcting agent, long alkyl chain length quaternary ammonium salt such as octadecyl-or palmityl trimethyl ammonium chloride or brometo de amonio and two hydrogenated-tallow group alkyl dimethyl ammonium chlorides be properties-correcting agent the most frequently used when preparing PLSN at present.Investigators begin to adopt the properties-correcting agent of double bond containing polymerizable alkylammonium salt as polynite recently.The double bond containing ammonium salt of this class mainly contains hexadecyldimethyl benzyl ammonium allyl group bromination ammonium, (to the vinyl benzene methyl) 12 (or 16) alkyl-dimethyl ammonium chloride etc.With this class properties-correcting agent polynite is uniformly dispersed, and and polymeric matrix between form stronger chemical bonding.But reaction is complicated, wayward, the cost height.
Surface coupling modification utilization has surface-active organo-functional group etc. and carries out chemisorption or reaction with the polynite surface, thereby make coupling agent be covered in the polynite surface to increase its dispersiveness in non-polar solvent, coupling agent commonly used has silicane, titante coupling agent etc.Kommann has reported with silane coupling agent and has handled polynite, enters the research for preparing unsaturated polyester/nano composite material between cheating engaging layer by the macromolecular chain intercalation again.Song report use C
18H
37SiCl
3And C
18H
37Si (OMe)
3The research of modified montmorillonoid by performances such as the specific surface area of modified montmorillonoid, interlamellar spacing are analyzed, has proved that the employed solvent of modifying process has material impact to modified effect.
Ogawa is to Trimethyllaurylammonium bromide (C
12TMA) the wheat hydroxyl silicon sodium stone of intercalation carries out the modification processing of chlorosilane, discovers that the use of chlorosilane can be carried out finishing and slightly influential to interlamellar spacing to the polynite of organic modification.
The open CN1468914A of Chinese patent application discloses a kind of preparation method of organic montmorillonoid, comprise the steps: the mixture of polynite, alkyl quaternary amine salt, polyoxyethylene glycol, ethanol, mineral acid and water was heated under 60～90 ℃ condition 0.5～6 hour, from solution, collect organic montmorillonoid then.The organic content of the organic montmorillonoid of this invention preparation reaches more than 20%, and the interfloor distance of polynite has obtained increase.The organic montmorillonoid of this invention is strong with the organic avidity that contains polar group, and the good dispersity in polar organic matter can be advantageously applied to preparation polymer/montmorillnoite nano material field.
The open CN1527798A of Chinese patent application discloses a kind of method that changes the surface of clay chemistry.In one embodiment, the method for change surface of clay chemistry comprises: the clay dispersion that contains at least a unmodified clay is provided, and wherein said clay has first exchangeable cation; Second positively charged ion is added in the clay dispersion, and wherein at least a portion second positively charged ion and at least a portion first cationic exchange generate the clay dispersion of modification; And at least a polar reagent and the modified clay dispersion liquid of containing merged, obtain modified clay.
Chinese patent CN1079409C (ZL98101496.8) adopts macromole emulsion intercalation method, earlier clay is dispersed in the water with lower ratio, adds rubber latex then, add flocculation agent at last whole system is condensed altogether, slough moisture, obtain rubber/clay nanocomposites.Nano composite materials such as clay/SBR, clay/NBR, clay/NR, clay/CR have successfully been prepared with this technology.This technology has made full use of most of rubber all this advantage of emulsion form of oneself, and technology is simple, and is easy to control, and cost is low.Shortcoming is when clay content is higher, and dispersed not as reactive intercalation method, wastewater flow rate is also bigger.
Open CN1458175A (the application number: ZL02117674.4) adopt in-situ inserted polymerization to prepare rubber/Nano composite material of montmorillonite first of Chinese patent application, the solvent that is adopted is a toluene, organic montmorillonoid is quaternary ammonium salt-modified through hexadecyl/octadecyl, but the dispersiveness of the polynite of this organic modification in non-polar solvent such as hexanaphthene is all relatively poor, can not form stable dispersion system, and using anionoid polymerization technology to produce in the industrial production of rubber at present, generally use non-polar solvents such as hexanaphthene, the present invention is just by modification has solved stable dispersion problem in non-polar solvent to the polynite surfaces externally and internally.
Summary of the invention
Based on above-mentioned prior art situation, the present inventor has carried out research extensively and profoundly in the Organophilic Modification of Montmorillonite field, in the hope of developing a kind of organic modification polynite of excellent dispersion in non-polar solvent, and further prepare rubber/Nano composite material of montmorillonite based on this new modified polynite.Found that modification has solved stable dispersion problem in non-polar solvent to the polynite surfaces externally and internally by using quaternary ammonium salt and coupling agent, and by adopting classical anionic solution polymerization method, realize the in-situ inserted polymerization of divinylic monomer, prepare a class polyhutadiene/Nano composite material of montmorillonite, improved the resistance toheat of polymeric articles effectively.The organic modification polynite of quaternary ammonium salt that the present invention adopts and the composite modified preparation of coupling agent has good dispersiveness in non-polar solvent, be easy to industrialization, this advantage of the present invention just place.In addition, the present invention utilizes polymer nanocomposites disperse phase height to become more meticulous and nanometer size effect improves the mechanical property and the functionalization ability of conventional composite materials, makes product have more outstanding characteristic.
The object of the present invention is to provide a kind of novel method of organic modification polynite, this method makes the surfaces externally and internally of polynite all reach hydrophobicity, thereby can in non-polar solvent such as hexanaphthene, have good and stable dispersion, be equipped with the purpose of polyhutadiene/Nano composite material of montmorillonite to realize in-situ inserted polymerization.
Another object of the present invention is to provide a kind of polyhutadiene/Nano composite material of montmorillonite, polyhutadiene/Nano composite material of montmorillonite of the present invention has excellent heat resisting more.
An also purpose of the present invention is to provide a kind of method for preparing polyhutadiene/Nano composite material of montmorillonite, comprises the preparation of the modified montmorillonoid that organises and the in-situ inserted polymerization of divinylic monomer.
Therefore, one aspect of the present invention relates to a kind of method of polynite being carried out intercalation and finishing, comprise and use cationite that intercalation modifying is carried out in polynite earlier, use coupling agent that surperficial coupling modification is carried out in the polynite of cation-intercalated modification then.
The present invention relates on the other hand by the cationite intercalation modifying of above-mentioned intercalation and surface modification method preparation and the polynite of coupling agent surface coupling modification.
Further aspect of the present invention relates to a kind of polyhutadiene/Nano composite material of montmorillonite, comprises polyhutadiene and the above-mentioned modified montmorillonoid that is scattered in wherein.
The present invention also relates in one aspect to a kind of method for preparing polyhutadiene/Nano composite material of montmorillonite, comprise as mentioned above intercalation and finishing are carried out in polynite, utilize the production technique of existing lithium system polybutadiene then, the in-situ inserted polymerization by divinylic monomer is equipped with polyhutadiene/Nano composite material of montmorillonite.
These and other purposes of the present invention, feature and advantage will become cheer and bright read the application's detailed description at the reference accompanying drawing after.
Description of drawings
Fig. 1 is the XRD spectra according to the quaternary ammonium salts modified montmorillonoid of embodiment 1-3 preparation.
Fig. 2 is the XRD spectra according to the coupling agent surface coupling modification 3C16-OMMT of embodiment 4-8 preparation.
Fig. 3 is the XRD spectra according to the polyhutadiene/Nano composite material of montmorillonite of embodiment 9-11 preparation.
Fig. 4 is the comparison according to quaternary ammonium salts modified montmorillonoid solute effect in hexanaphthene of embodiment 1-3 preparation.
Fig. 5 is the comparison according to coupling agent surface coupling modified montmorillonoid solute effect in hexanaphthene of embodiment 4-8 preparation.
Embodiment
In montmorillonite intercalation of the present invention and surface modification method, the first step relates to uses cationite that intercalation modifying is carried out in polynite, with the interlayer chemical environment of modified montmorillonoid.For intercalation modifying is carried out in polynite, usually with natural montmorillonite under agitation with the 0.5-10 weight part, the ratio of preferred 1-5 weight part/100ml is scattered in the dispersion medium, forms stable montmorillonite suspension liquid.In addition, individually with cationite with the 0.5-15 weight part, the ratio of preferred 1-10 weight part/100ml is dissolved in the dispersion medium, forms solution.At 50-100 ℃, under preferred 60-85 ℃ the temperature this solution is added in the montmorillonite suspension liquid then, stirred 1-8 hour, preferred 3-6 hour, suction filtration and washing 60 ℃ of following vacuum-dryings, made the polynite of cationite intercalation modifying then.
In this first step, stirring velocity is unimportant, as long as can realize the abundant dispersion of polynite in dispersion medium.Yet, preferably carry out high-speed stirring.
In this first step, washing uses distilled water to carry out usually 3-5 time.Contain the situation of bromide anion or chlorion for cationite, whether washing the abundant AgNO by use 0.1mol/L
3Whether contain bromide anion or chlorion in the aqueous assay washing water.
In montmorillonite intercalation of the present invention and surface modification method, second step related to uses coupling agent that surperficial coupling modification is carried out in the polynite of cation-intercalated modification, so that the polynite surfaces externally and internally all reaches hydrophobicity, thereby can in non-polar solvent such as hexanaphthene, obtain good and stable dispersion, be equipped with the purpose of polyhutadiene/Nano composite material of montmorillonite to realize in-situ inserted polymerization.For the first step products therefrom being carried out surperficial coupling modification, usually will be 60-90 ℃ temperature and under stirring from the polynite of the cationite intercalation modifying of the first step with the 0.5-10 weight part, the ratio of preferred 1-5 weight part/100ml is scattered in the 100 weight part dispersion medium, and to add based on the polynite from the cationite intercalation modifying of the first step in whipping process be 0.1-10 weight %, the coupling agent of preferred 0.5-5 weight %, continue then to stir 10-90 minute, preferred 10-30 minute, remove dispersion medium, vacuum-drying makes the polynite of cationite intercalation modifying and surperficial coupling modification.
In montmorillonite intercalation of the present invention and finishing, the preferred mineralogical composition content of used polynite is no less than the layered silicate of 85% polynite, more preferably mineralogical composition content is no less than the layered silicate of 95% polynite, its unit cell is made up of folder layer of aluminum oxygen octahedra in the two-layer silicon-oxy tetrahedron, connect by shared Sauerstoffatom between the two, cheating engaging layer inner surface belt negative charge, interlayer has Na
+, Ca
2+, Mg
2+Etc. the interchangeability positively charged ion, through the dispersion of delaminating, the remodeling of purifying, ultra-fine dispersion forms.The cationic exchange total volume (CEC) of described polynite is 50-200meq/100g, and particle size range is 1-70 μ m.More preferably the cationic exchange total volume (CEC) of polynite is 90-120meq/100g, and particle size range is 20-30 μ m.
In montmorillonite intercalation of the present invention and finishing, used cationite is the quaternary ammonium salt shown in the following general formula:
R wherein
1, R
2, R
3Identical or different and independently for having the saturated or unsaturated alkyl of 1-24 carbon atom or having the aryl of 7-10 carbon atom, R
4Be the alkyl with 1-6 carbon atom or the aryl of 7-10 carbon atom, X is OH, Cl, Br, I, NO
3This examples for compounds has Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, INCROQUAT TMC-80, two dodecyl dimethyl ammonium chlorides, two tetradecyl alkyl dimethyl ammonium chlorides, Varisoft 432PPG, distearyl dimethyl ammonium chloride, two hydrogenated-tallow group alkyl dimethyl ammonium chlorides, three (dodecyl) ammonio methacrylate, three (tetradecyl) ammonio methacrylate, three (hexadecyl) ammonio methacrylate, three (octadecyl) ammonio methacrylate, or corresponding bromide, it can be used alone or as a mixture.
In montmorillonite intercalation of the present invention and finishing, used coupling agent comprises titanate coupling agent, silane coupling agent, aluminium titanium composite coupler etc.
The general structure of preferred titanate coupling agent is as follows:
(R
1O)
m-(Ti-OX
1-R′-Y
1)
n，
1≤m≤4 wherein; M+n≤6; R
1Saturated alkyl for the 1-4 carbon atom; R ' is the saturated alkyl of 1-24 carbon atom or the aryl of 7-20 carbon atom; X
1Be groups such as C=O, O-P=O; Y
1Be groups such as hydroxyl, amino, epoxy group(ing), alkenyl.This examples for compounds has two fat acyloxy metatitanic acid second diester, isopropoxy tricarboxylic acyl titanate, two (dioctylphosphato) metatitanic acid second diester.
The general structure of preferred silane coupling agent is as follows:
Y
2-(CH
2CH
2-)
o-Si-X
2 3，
Wherein o is 2～30, Y
2Be organo-functional group, as vinyl, methacryloyl, epoxy group(ing), amino, sulfydryl etc.; X
2Be hydrolysable group, as halogen, alkoxyl group, acyloxy etc.This examples for compounds has long-chain saturated alkane silane coupling agent (8-30 carbon atom), γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan, γ-(methacryloxypropyl) oxypropyl trimethyl oxosilane.
The general structure of preferred aluminium titanium composite coupler is as follows:
R wherein
3Saturated or unsaturated alkane for 1-24 carbon atom.This examples for compounds has YT-05 (it is on sale that trade(brand)name, Shandong Zibo easily join chemical industry company limited), OL-AT1618 (trade(brand)name, the Shanxi chemical institute is on sale).
In montmorillonite intercalation of the present invention and finishing, employed dispersion medium is water, sherwood oil, toluene, acetone, ethanol.
In montmorillonite intercalation according to the present invention and surface modification method, the interlamellar spacing of the polynite of the cationite intercalation modifying that is obtained by the first step is 2.0-5.5nm, and the coupling agent finishing in second step can not produce remarkable influence to the interlamellar spacing of polynite, and promptly the interlamellar spacing of the modified montmorillonoid that is obtained by second step is 2.0-5.5mm.
By carrying out intercalation and finishing as mentioned above, the gained modified montmorillonoid can stably be scattered in the organic solvent, and is particularly in non-polar organic solvent such as the hexanaphthene, dispersions obtained even can stablize more than 24 hours.
Polyhutadiene/Nano composite material of montmorillonite according to the present invention comprises polyhutadiene and the modified montmorillonoid of the present invention that is scattered in wherein, and wherein the number-average molecular weight scope of polyhutadiene is 1-60 * 10
4, preferred 1-3 * 10
5, modified montmorillonoid content is 0.5-50 weight part/100 weight part polyhutadiene, more preferably 0.5-15 weight part/100 weight part polyhutadiene.
Polyhutadiene/Nano composite material of montmorillonite of the present invention is prepared by a method comprising the following steps:
A) cationite is to the intercalation modifying of polynite: under agitation with the 0.5-10 weight part, the ratio of preferred 1-5 weight part/100ml is scattered in the dispersion medium, forms stable montmorillonite suspension liquid with natural montmorillonite; Individually with cationite with the 0.5-15 weight part, the ratio of preferred 1-10 weight part/100ml is dissolved in the dispersion medium, forms solution; At 50-100 ℃, under preferred 60-85 ℃ the temperature this solution is added in the montmorillonite suspension liquid, stirred 1-8 hour, preferred 3-6 hour, suction filtration and washing 60 ℃ of following vacuum-dryings, made the polynite of cationite intercalation modifying then;
B) coupling agent is to the surperficial coupling modification of the product of step a): will be from the polynite of the cationite intercalation modifying of the first step with the 0.5-10 weight part 60-90 ℃ temperature and under stirring, the ratio of preferred 1-5 weight part/100ml is scattered in the 100 weight part dispersion medium, and to add based on the polynite from the cationite intercalation modifying of the first step in whipping process be 0.1-10 weight %, the coupling agent of preferred 0.5-5 weight %, continue then to stir 10-90 minute, preferred 10-30 minute, remove dispersion medium, vacuum-drying makes the polynite of cationite intercalation modifying and surperficial coupling modification;
C) modified montmorillonoid that step b) is obtained joins in the dispersion medium, it is even to be stirred to system, be made into the organic modification montmorillonite dispersions, wherein the proportioning of the dispersion liquid of organic modification polynite is 1-10 weight part organic modification polynite/100ml dispersion medium;
D) hydrocarbon organic solvent, divinyl, optional polar additive and the organic modification montmorillonite dispersions of step c) are added in the reactor, evenly stir, form stable divinyl/organic modification montmorillonite dispersions, be warming up to 30-80 ℃, add organic lithium initiator, begin to carry out polyreaction, wherein the consumption of organic lithium initiator is selected according to the size of required polyhutadiene number-average molecular weight;
E) after the divinyl total overall reaction finishes, add terminator, stop polyreaction, and randomly add conventional additives, adopt traditional method that the polymkeric substance glue is carried out aftertreatment then, obtain polyhutadiene/Nano composite material of montmorillonite behind the product drying.
In the method for preparing polyhutadiene/Nano composite material of montmorillonite of the present invention, step a) and step b) are corresponding to the first step in montmorillonite intercalation of the present invention and the surface modification method and second step, and its details here repeat no more.
In the method for preparing polyhutadiene/Nano composite material of montmorillonite of the present invention, dispersion medium that uses in the step c) and d) in the hydrocarbon organic solvent that uses identical.
In the method for preparing polyhutadiene/Nano composite material of montmorillonite of the present invention, the hydrocarbon organic solvent that uses in the step d) is selected from a kind of varsol of aromatic hydrocarbons and aliphatic hydrocarbon or the mixture of several varsols, generally be selected from benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinate oil etc., be preferably selected from hexanaphthene, toluene, dimethylbenzene, hexane, raffinate oil.It is 5-30 weight % that solvent load should make the concentration of monomer divinyl.
In the method for preparing polyhutadiene/Nano composite material of montmorillonite of the present invention, the polar additive that uses in the step d) is selected from and contains oxygen, nitrogenous, sulfur-bearing, contains a kind of polar compound in the Phosphorus polar compound or the mixture of several polar compounds, as: (1) oxygenatedchemicals generally is selected from ether, tetrahydrofuran (THF), R
1OCH
2CH
2OR
2(R wherein
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical or different, with R
1, R
2Be not all good, as ethylene glycol diethyl ether), R
1OCH
2CH
2OCH
2CH
2OR
2(R wherein
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical or different, with R
1, R
2Be not all good, as diethylene glycol dibutyl ether); (2) nitrogenous compound generally is selected from: triethylamine, Tetramethyl Ethylene Diamine (TMEDA), two piperidines ethane, preferred TMEDA; (3) P contained compound is generally selected HMPA for use.The consumption of polar additive is regulated according to the content of required vinyl structure.
In the method for preparing polyhutadiene/Nano composite material of montmorillonite of the present invention, the initiator that uses in the step d) is organic lithium initiator, is selected from the mixture of simple function group organolithium, bifunctional organolithium, polyfunctional group organolithium or several organic lithium initiators.Organic lithium initiator can be represented by the formula: R (Li) x, and R is the alkyl that contains 1-20 carbon atom, and R can be alkyl or aryl, and x is the integer of 1-8.
Initiator used in the present invention can be the disclosed any simple function group organic lithium initiator of prior art, be selected from a kind of simple function group organic lithium initiator or its mixture, generally be selected from: lithium methide, lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, uncle's octyl group lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-phenyl butyl lithium, cyclohexyl lithium.
Initiator used in the present invention also can be the disclosed any bifunctional organic lithium initiator of prior art, be selected from a kind of bifunctional organic lithium initiator or its mixture, generally be selected from: two lithiums of (1) two haloalkane hydro carbons and the two lithiums of oligopolymer thereof, its structural formula is LiRLi, Li (DO) nR (DO) nLi, wherein: R is that carbonatoms is the alkyl of 4-10, DO is that carbonatoms is a kind of conjugated diene of 4-8 or the mixture of several conjugated dienes, with 1, the 3-divinyl, isoprene is good, n is the oligomerisation degree, and n is generally 2-8, is good with 3-6, two lithiums of two haloalkane hydro carbons and the two lithiums of oligopolymer thereof generally are selected from: 1,4-two lithium butane, 1,2-two lithiums-1,2-diphenylethane, 1,4-two lithiums-1,1,4,4-tetraphenyl butane, 1,4-dimethyl-1,4-diphenyl butane two lithiums, polyhutadiene two lithium oligopolymers, polyisoprene two lithium oligopolymers; (2) the two lithiums of naphthalene class generally are selected from: naphthalene lithium, alpha-methyl-naphthalene lithium; (3) two lithiums of diene hydro carbons and the two lithiums of oligopolymer thereof, generally be selected from: 1,1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1,1 '-(1, the 3-penylene)-two two lithiums, 1 of [3-methyl isophthalic acid-(4-tolyl) amyl group] butadiene oligomer, 1 '-(1, the 3-penylene)-two two lithiums, 1 of [3-methyl isophthalic acid-(4-tetraphenyl) amyl group] isoprene oligopolymer, 1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1, the two lithiums of 1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer.
Initiator used in the present invention also can be the disclosed any multifunctional group organic lithium initiator of prior art, be selected from a kind of multifunctional group organic lithium initiator, be selected from the mixture of a kind of multifunctional group organic lithium initiator or several multifunctional group organic lithium initiators, as R
#Li
n, T (R
#Li)
n, wherein: R
#For carbonatoms is the alkyl of 4-20, R
#Can be alkyl or aryl, T be an atoms metal, is generally metallic elements such as tin Sn, silicon Si, plumbous Pn, titanium Ti, germanium Ge, and n is the initiator functionality, and n is more than or equal to 3, and n is generally at 3-150, and preferred range is at 3-50, and optimum range is at 3-10.The polyfunctional group lithium initiator can be a multi-chelate organolithium initiator, reacts the various multi-chelate organolithium initiators that obtain as Vinylstyrene (DVB) and the lithium alkylide of mentioning in the patents such as GB2124228A, US3280084, EP0573893A2, CN1197806A.Polyfunctional group lithium initiator R
#Li
nCan be to contain above-mentioned class multifunctional group organic lithium initiator T (R
#Li)
n, multifunctional initiator T (R
#Li)
nGenerally be selected from stanniferous class multifunctional group organic lithium initiator Sn (R
#Li)
n, as the stanniferous class multifunctional group organic lithium initiator Sn (R that mentions among the patent CN1148053
#Li)
4The polyfunctional group lithium initiator can also be that other functionality that can be used in initiation divinyl, isoprene equiconjugate diolefine and styrene monomer is not less than 3 polyfunctionality organic lithium initiator, as the various multifunctional group organic lithium initiators of mentioning among patent US5262213, the US5595951.
In the method for preparing polyhutadiene/Nano composite material of montmorillonite of the present invention, in the step d) consumption of organic lithium initiator be generally cause polyhutadiene polymerization theory consumption 1-10 doubly.
In the method for preparing polyhutadiene/Nano composite material of montmorillonite of the present invention, the consumption of divinyl and organic modification polynite should make that the ratio of polyhutadiene and organic modification polynite is 0.5-50 weight part organic modification polynite/100 weight parts of butadiene in the gained matrix material, preferred 0.5-15 weight part organic modification polynite/100 weight parts of butadiene.
In the method for preparing polyhutadiene/Nano composite material of montmorillonite of the present invention, the terminator in the step e) is generally dehydrated alcohol, Virahol etc., can be used alone or as a mixture, and its consumption is generally the 1-5% that needs the trigger monomer quality.
In the method for preparing polyhutadiene/Nano composite material of montmorillonite of the present invention, the optional additive that uses for example is commonly used those in this area in step e), usually add anti-aging agent such as Irganox1010 (trade(brand)name, Ciba-Geigy company is on sale), Antigene BHT or 2.6.4 (trade(brand)name, SUMITOMO CHEMICAL KCC is on sale) or its mixture.The consumption of anti-aging agent can be commonly used those in this area, and being preferably based on the amount for the treatment of the polymerization divinyl is 0.1-10 weight %.
Embodiment
The present invention is described in detail by the following example, but these embodiment are not limited to scope of the present invention.
In the following embodiments, the performance of products obtained therefrom is tested as follows:
XRD：
Japan D/ma of science * RB type, 12KW X ray remember spectrum scanning, CuK α radiation, back monochromator, tube voltage 40kV, tube current 100mA, 1～15 ° of sweep limit, 2 °/minute of sweep velocitys continuously.
TGA：
Adopt NETZSCH TG 209 thermal gravimetric analyzers, temperature range: 40 ℃-700 ℃, temperature rise rate: 10K/ minute, N
2Environment.
Thermal weight loss core temperature Tdc:
Adopt NETZSCH TG 209 thermal gravimetric analyzers, temperature range: 40 ℃-700 ℃, temperature rise rate: 10K/ minute, N
2Environment
Microstructure of Polybutadiene
Adopt the U.S. NMR of BRUKE company analyser.
Molecular weight and molecular weight distribution
The Maxims of U.S. waters company 820 type liquid phase gel permeation chromatography GPC.
Solubility test:
Under the room temperature, polynite of cationite intercalation modifying and coupling agent surface-treated organic modification polynite (OMMT) are dispersed in the hexanaphthene, being made into concentration is the hexanaphthene dispersion of 4g OMMT/100g, pour into respectively in the 25ml test tube, keep the liquid level unanimity, note the settling time of each sample solution.
The nano imvite that is adopted among the following embodiment (fine powder body) reaches and is provided by Zhejiang Feng Hong clay chemical industry company limited, product grade is NANNOLIN DK0, polynite content is 95-98 weight %, median size is 25 μ m, average wafer thickness is less than 25nm, the humidity amount is less than 3 weight %, and cation exchange capacity is 110meq/100g, and interlamellar spacing is 1.54nm.Contrast sample product grade is NANNOLIN DK1B, is also provided by Zhejiang Feng Hong clay chemical industry company limited, and interlamellar spacing is 3.13nm, and the solubility test result is presented at layering in 15 minutes in the hexanaphthene.Cetyl trimethylammonium bromide (C16), two hydrogenated-tallow group alkyl dimethyl ammonium chlorides and three (hexadecyl) ammonio methacrylate are provided by Feixiang Chemical Co., Ltd., Jiangsu; Coupling agent CT-201 (two fat acyloxy metatitanic acid second diester), CT-101 (isopropoxy tricarboxylic acyl titanate), CT-104 (two (dioctylphosphato)) metatitanic acid second diester), KH-560 (γ-glycidyl ether oxygen propyl trimethoxy silicane) provides by the sharp evolution worker in changzhou company limited; Aluminium titanium composite coupler YT-05 easily joins chemical industry company limited by Shandong Zibo to be provided.The organic modification montmorillonite dispersions is that the organic modification polynite is added in the dispersion medium (concentration is the 4gOMMT/100ml dispersion medium), obtains after stirring.
Embodiment 1
Claim 2.5g polynite (DK0), be scattered in the 100ml deionized water, stir, be warmed up to 60 ℃, obtain a suspension.In addition, individually 1.0g cetyl trimethylammonium bromide (C16) is added in the 50ml deionized water wiring solution-forming.Then this solution is added in the montmorillonite suspension liquid, vigorous stirring, insulation (60 ℃) is 4 hours in the water-bath, and suction filtration is with distilled water wash cationite intercalation modifying polynite 3-5 time, until the AgNO with 0.1mol/L
3Aqueous assay is less than Br
-, 60 ℃ of following vacuum-dryings make C16-OMMT (OMMT1).XRD the results are shown in Figure 1 curve b, detects the diffraction peak that shows the polynite of cationite intercalation modifying and moves to low angle, and interlamellar spacing increases, and interlamellar spacing is 2.04nm by the 1.54nm increase of DK0, shows that quaternary ammonium salt has inserted montmorillonite layer.
Embodiment 2
Claim the 2.5g polynite, be scattered in the 100ml deionized water, stir, be warmed up to 60 ℃, obtain a suspension.In addition, individually the two hydrogenated-tallow group alkyl dimethyl ammonium chlorides (2C16-18) of 2.2g are added in the 50ml deionized water wiring solution-forming.Then this solution is added in the montmorillonite suspension liquid, vigorous stirring, insulation (60 ℃) is 4 hours in the water-bath, and suction filtration is with distilled water wash cationite intercalation modifying polynite 3-5 time, until the AgNO with 0.1mol/L
3Aqueous assay is less than Cl
-, 60 ℃ of following vacuum-dryings make 2 (C16-18)-OMMT (OMMT1).XRD the results are shown in Figure 1 curve c, detects the diffraction peak that shows the polynite of cationite intercalation modifying and moves to low angle, and interlamellar spacing increases, and interlamellar spacing is 3.40nm by the 1.54nm increase of DK0, shows that quaternary ammonium salt has inserted montmorillonite layer.
Embodiment 3
Claim the 2.5g polynite, be scattered in the 100ml deionized water, stir, be warmed up to 60 ℃, obtain a suspension.In addition, individually 3.0g three (hexadecyl) ammonio methacrylate (3C16) is added in the 50ml deionized water wiring solution-forming.Then this solution is added in the montmorillonite suspension liquid, vigorous stirring, insulation (60 ℃) is 4 hours in the water-bath, and suction filtration is with distilled water wash cationite intercalation modifying polynite 3-5 time, until the AgNO with 0.1mol/L
3Aqueous assay is less than Cl
-, 60 ℃ of following vacuum-dryings make 3C16-OMMT (OMMT1).XRD the results are shown in Figure 1 curve d, detects the diffraction peak that shows the polynite of cationite intercalation modifying and moves to low angle, and interlamellar spacing increases, and interlamellar spacing is 5.07nm by the 1.54nm increase of DK0.As seen from Figure 1, the interlamellar spacing of 3C16-OMMT is maximum among Fig. 1, and greater than the 3.13nm that contrasts sample DK1B.The solubility test result shows, tangible layering (f in as Fig. 4) just appears in 3C16-OMMT after greater than 1.5 hours, than C16-OMMT (layering in 10 minutes) (as among Fig. 4 a), the solute effect of 2 (C16-18)-OMMT (layering in 20 minutes) (as e among Fig. 4), DK1B (layering in 15 minutes) (as b among Fig. 4) is all good, c among Fig. 4, d are respectively 2 (C16-18)-OMMT, the 3C16-OMMT effects when disperseing 30 minutes in hexanaphthene.Based on above result, select for use 3C16-OMMT further to carry out the coupling agent finishing.
Embodiment 4
Method according to embodiment 3 prepares 3C16-OMMT; under agitation 3C16-OMMT powder 2.5g is scattered in the sherwood oil of 50 ℃ of 60ml; and in whipping process, add 0.1g CT-101 (isopropoxy tricarboxylic acyl titanate); stir and slough solvent after 30 minutes; 60 ℃ of following vacuum-dryings make 3C16-OMMT-(4%CT-101) (OMMT2).XRD the results are shown in Figure 2 curve b, detecting the diffraction peak that shows the modified montmorillonoid that organises moves to low angle, interlamellar spacing is 5.19nm (OMMT2) by the 1.54nm increase of DK0, is significantly higher than the interlamellar spacing 3.13nm of contrast sample DK1B, and is close with the interlamellar spacing (5.07nm) of 3C16-OMMT; Solubility test shows, obvious layering appears 1.5 hours the time in 3C16-OMMT in hexanaphthene, obvious layering (as b among Fig. 5) appears in 3C16-OMMT-(4%CT-101) when dissolving 7 hours in hexanaphthene, be significantly higher than the obviously layering in 15 minutes of contrast sample DK1B.The result shows that the adding of coupling agent CT-101 has further improved the hydrophobicity of polynite, and does not change the original intercalation configuration of montmorillonite layer.
Claim the 2.5g polynite, be scattered in the 100ml deionized water, stir, be warmed up to 60 ℃, obtain a suspension.In addition, individually 3.0g three (hexadecyl) ammonio methacrylate (3C16) is added in the 50ml deionized water wiring solution-forming.Then this solution is added in the montmorillonite suspension liquid, vigorous stirring, insulation (60 ℃) is 3.5 hours in the water-bath, add 0.1g CT-201 (two fat acyloxy metatitanic acid second diester) then, stirred 30 minutes, suction filtration is with distilled water wash organic modification polynite 3-5 time, until the AgNO with 0.1mol/L
3Aqueous assay is less than Cl
-, 60 ℃ of following vacuum-dryings make 3C16-OMMT-(4%CT-201).XRD the results are shown in Figure 2 curve c, and interlamellar spacing is 5.07nm (3C16-OMMT) and 5.19nm (3C16-OMMT-(4%CT-201)) by the 1.54nm increase of DK0, is significantly higher than the interlamellar spacing 3.13nm of contrast sample DK1B; Solubility test shows, 3C16-OMMT-(4%CT-201) in hexanaphthene, do not occur in 24 hours obvious layering (as among Fig. 5 a), form steady suspension, be significantly higher than the obviously layering in 15 minutes of contrast sample DK1B.The result shows that the adding of coupling agent CT-201 has further improved the hydrophobicity of polynite, and does not change the original intercalation configuration of montmorillonite layer.
Embodiment 6
Method according to embodiment 3 prepares 3C16-OMMT, under agitation 3C16-OMMT powder 2.5g is scattered in the acetone of 70 ℃ of 60ml, and in whipping process, add 0.1g KH-560 (γ-glycidyl ether oxygen propyl trimethoxy silicane), stir and slough solvent after 30 minutes, vacuum-drying makes 3C16-OMMT-(4%KH-560).XRD spectra is seen the curve d of Fig. 2, and interlamellar spacing is 5.19nm (3C16-OMMT-(4%KH-560)) by the 1.54nm increase of DK0, is significantly higher than the interlamellar spacing 3.13nm of contrast sample DK1B; Solubility test shows that obvious layering (as e among Fig. 5) appears in 3C16-OMMT-(4%KH-560) when dissolving 3 hours in hexanaphthene, is significantly higher than the obviously layering in 15 minutes of contrast sample DK1B.The result shows that the adding of coupling agent KH-560 has further improved the hydrophobicity of polynite, and does not change the original intercalation configuration of montmorillonite layer.
Embodiment 7
Claim the 2.5g polynite, be scattered in the 100ml deionized water, stir, be warmed up to 60 ℃, obtain a suspension.In addition, independently 3.0g three (hexadecyl) ammonio methacrylate (3C16) is added in the 50ml deionized water wiring solution-forming.Then this solution is added in the montmorillonite suspension liquid, vigorous stirring, insulation (60 ℃) is 3.5 hours in the water-bath, add 0.1g CT-104 (two (dioctylphosphato)) metatitanic acid second diester then), stirred 30 minutes, suction filtration is with deionized water wash organic modification polynite 3-5 time, until the AgNO with 0.1mol/L
3Aqueous assay is less than Cl
-, 60 ℃ of following vacuum-dryings make 3C16-OMMT-(4%CT-104).XRD the results are shown in Figure 2 curve e, and interlamellar spacing is 5.07nm (3C16-OMMT) and 5.10nm (3C16-OMMT-(4%CT-104)) by the 1.54nm increase of DK0, is significantly higher than the interlamellar spacing 3.13nm of contrast sample DK1B; Solubility test shows that obvious layering (as d among Fig. 5) does not appear in 3C16-OMMT-(4%CT-104) in 14 hours in hexanaphthene, is significantly higher than the obviously layering in 15 minutes of contrast sample DK1B.The result shows that the adding of coupling agent CT-104 has further improved the hydrophobicity of polynite, and does not change the original intercalation configuration of montmorillonite layer.
Embodiment 8
Claim the 2.5g polynite, be scattered in the 100ml deionized water, stir, be warmed up to 60 ℃, obtain a suspension.In addition, individually 3.0g three (hexadecyl) ammonio methacrylate (3C16) is added in the 50ml deionized water wiring solution-forming.Then this solution is added in the montmorillonite suspension liquid, vigorous stirring, insulation (60 ℃) is 3.5 hours in the water-bath, adds 0.1g YT-05 then, stirs 30 minutes, and suction filtration is with deionized water wash organic modification polynite 3-5 time, until the AgNO with 0.1mol/L
3Aqueous assay is less than Cl
-, 60 ℃ of following vacuum-dryings make 3C16-OMMT-(4%YT-05).XRD the results are shown in Figure 2 curve f, and interlamellar spacing is 4.9nm (3C16-OMMT-(4%YT-05)) by the 1.54nm increase of DK0, is significantly higher than the interlamellar spacing 3.13nm of contrast sample DK1B; Solubility test shows that 3C16-OMMT-(4%YT-05) obvious layering occurs when disperseing 3 hours in hexanaphthene, is higher than the obviously layering (c in as Fig. 5) in 15 minutes of contrast sample DK1B.The result shows that the adding of coupling agent YT-05 has further improved the hydrophobicity of polynite, and does not change the original intercalation configuration of montmorillonite layer.
Embodiment 9
In the 500ml reactor, add 64g hexanaphthene and 8g divinyl, 3C16-OMMT-(4%CT-201) dispersion liquid (4g organic modification polynite/100ml hexanaphthene) that adds 4ml again, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.4ml (0.2011M cyclohexane solution), react and add terminator 0.24g dehydrated alcohol after 6 hours, add 0.08g (is 1% based on monomer mass) anti-aging agent (1010 with mass ratio 1: 1 mix with 2.6.4) then, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, test behind the product drying, obtain polyhutadiene/Nano composite material of montmorillonite.Polyhutadiene/Nano composite material of montmorillonite design molecular weight is 100,000, and gained sample Mn is that 10.6 ten thousand, Mw/Mn are 1.28.The thermal weight loss core temperature of product polyhutadiene/Nano composite material of montmorillonite is 482.1 ℃, and apparently higher than 460.2 ℃ of the thermal weight loss core temperatures of Comparative Examples, and organic modification polynite content is 2.0 weight %.XRD the results are shown in Figure 3 curve a, detect to show the diffraction peak completely dissolve of polynite, shows that the organo montmorillonite lamella peels off each other, separates fully, is state of disarray and is dispersed in the polyhutadiene matrix.Therefore this matrix material is an exfoliated nano-composite.
In the 500ml reactor, add 64g hexanaphthene and 8g divinyl, 3C16-OMMT-(4%CT-201) dispersion liquid (4g organic modification polynite/100ml hexanaphthene) that adds 8ml again, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.4ml (0.2011M cyclohexane solution), react and add terminator 0.24g dehydrated alcohol after 6 hours, add 0.08g (is 1% based on monomer mass) anti-aging agent (1010 with mass ratio 1: 1 mix with 2.6.4) then, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, test behind the product drying, obtain polyhutadiene/Nano composite material of montmorillonite.The design molecular weight is 100,000, and gained sample Mn is 9.5 ten thousand, and Mw/Mn is 1.3.The thermal weight loss core temperature of product polyhutadiene/Nano composite material of montmorillonite is 484.0 ℃, be significantly higher than 460.2 ℃ of the thermal weight loss core temperatures of Comparative Examples, and organo montmorillonite content is 4.0 weight %.XRD spectra is seen the curve b of Fig. 3, detect to show the diffraction peak completely dissolve of polynite, shows that the organo montmorillonite lamella peels off each other, separates fully, is state of disarray and is dispersed in the polyhutadiene matrix.Therefore, this matrix material is an exfoliated nano-composite.
Embodiment 11
In the 500ml reactor, add 64g hexanaphthene and 8g divinyl, 3C16-OMMT-(4%CT-104) dispersion liquid (4g organic modification polynite/100ml hexanaphthene) that adds 8ml again, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.4ml (0.2011M cyclohexane solution), react and add terminator 0.24g dehydrated alcohol after 6 hours, add 0.08g (is 1% based on monomer mass) anti-aging agent (1010 with mass ratio 1: 1 mix with 2.6.4) then, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, test behind the product drying, obtain polyhutadiene/Nano composite material of montmorillonite.The thermal weight loss core temperature of product polyhutadiene/Nano composite material of montmorillonite is 479.0 ℃, is significantly higher than 460.2 ℃ of the thermal weight loss core temperatures of Comparative Examples, and organic modification polynite content is 4.0 weight %.XRD the results are shown in Figure 3 curve c, detect to show the diffraction peak completely dissolve of polynite, shows that the organo montmorillonite lamella peels off each other, separates fully, is state of disarray and is dispersed in the polyhutadiene matrix.Therefore, this matrix material is an exfoliated nano-composite.
Embodiment 12
In the 500ml reactor, add 64g hexanaphthene and 8g divinyl, 3C16-OMMT-(4%CT-201) dispersion liquid (4g organic modification polynite/100ml hexanaphthene) that adds 8ml again, begin to stir, heating and constant temperature are at 50 ℃, add polar additive Tetramethyl Ethylene Diamine (TMEDA), TMEDA/Li (mol ratio) is 0.3, add and cause required n-Butyl Lithium 0.4ml (0.2011M cyclohexane solution), react and add terminator 0.24g dehydrated alcohol after 6 hours, add 0.08g (is 1% based on monomer mass) anti-aging agent (1010 with mass ratio 1: 1 mix with 2.6.4) then, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, test behind the product drying, obtain polyhutadiene/Nano composite material of montmorillonite.1,2 structural content of product polyhutadiene/Nano composite material of montmorillonite is 44.0 weight %, and 1,4 structural content is 66.0 weight %, and organic modification polynite content is 4.0 weight %.
Embodiment 13
In the 500ml reactor, add 64g hexanaphthene and 8g divinyl, 3C16-OMMT-(4%CT-201) dispersion liquid (4g organic modification polynite/100ml hexanaphthene) that adds 8ml again, begin to stir, heating and constant temperature are at 50 ℃, add polar additive Tetramethyl Ethylene Diamine (TMEDA), TMEDA/Li (mol ratio) is 1.2, add and cause required n-Butyl Lithium 0.4ml (0.2011M cyclohexane solution), react and add terminator 0.24g dehydrated alcohol after 6 hours, add 0.08g (is 1% based on monomer mass) anti-aging agent (1010 with mass ratio 1: 1 mix with 2.6.4) then, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, test behind the product drying, obtain polyhutadiene/Nano composite material of montmorillonite.1,2 structural content of product polyhutadiene/Nano composite material of montmorillonite is 65.0 weight %, and 1,4 structural content is 35.0 weight %, and organic modification polynite content is 4.0 weight %.
Comparative Examples 1
In the 500ml reactor, add 64g hexanaphthene and 8g divinyl, do not add the organo montmorillonite dispersion liquid, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.4ml (0.2011M cyclohexane solution), react and add terminator 0.24g dehydrated alcohol after 6 hours, add 0.08g (is 1% based on monomer mass) anti-aging agent (1010 with mass ratio 1: 1 mix with 2.6.4) then, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, test behind the product drying, obtain polybutadiene rubber.Product polyhutadiene 1,2 structural content is 11.6 weight %, and 1,4 structural content is 88.4 weight %, and glass transition temperature Tg is-89.6 ℃, and the thermal weight loss core temperature is 460.2 ℃.
Claims (11)
1. the surface modification method of a class polynite comprises the steps:
A) cationite is to the intercalation modifying of polynite: under agitation with the 0.5-10 weight part, the ratio of preferred 1-5 weight part/100ml is scattered in disperses to form stable montmorillonite suspension liquid in the dispersion media with natural montmorillonite; Individually with cationite with the 0.5-15 weight part, the ratio of preferred 1-10 weight part/100ml is dissolved in the dispersion medium, forms solution; At 50-100 ℃, under preferred 60-85 ℃ the temperature this solution is added in the montmorillonite suspension liquid, stirred 1-8 hour, preferred 3-6 hour, suction filtration and washing 60 ℃ of following vacuum-dryings, made the polynite of cationite intercalation modifying then; With
B) coupling agent is to the surperficial coupling modification of the product of step a): will be from the polynite of the cationite intercalation modifying of the first step with the 0.5-10 weight part 60-90 ℃ temperature and under stirring, the ratio of preferred 1-5 weight part/100ml is scattered in the 100 weight part dispersion medium, and to add based on the polynite from the cationite intercalation modifying of the first step in whipping process be 0.1-10 weight %, the coupling agent of preferred 0.5-5 weight %, continue then to stir 10-90 minute, preferred 10-30 minute, remove dispersion medium, vacuum-drying makes the polynite of cationite intercalation modifying and surperficial coupling modification.
2. according to the method for claim 1, it is characterized in that described polynite is that unit cell is made up of folder layer of aluminum oxygen octahedra in the two-layer silicon-oxy tetrahedron, connect by shared Sauerstoffatom between the two, cheating engaging layer inner surface belt negative charge, interlayer has Na
+, Ca
2+, Mg
2+Etc. the interchangeability positively charged ion, and mineralogical composition content is no less than 85%, preferably is no less than the layered silicate of 95% polynite, its cationic exchange total volume (CEC) 50-200meq/100g, preferred 90-120meq/100g, its particle size range is 1-70 μ m, preferred 20-30 μ m.
3. according to the method for claim 1, it is characterized in that described cationite is the quaternary ammonium salt shown in the following general formula:
R wherein
1, R
2, R
3Identical or different and independently for having the saturated or unsaturated alkyl of 1-24 carbon atom or having the aryl of 7-10 carbon atom, R
4Be the alkyl with 1-6 carbon atom or the aryl of 7-10 carbon atom, X is OH, Cl, Br, I, NO
2Preferred Dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, INCROQUAT TMC-80, two dodecyl dimethyl ammonium chlorides, two tetradecyl alkyl dimethyl ammonium chlorides, Varisoft 432PPG, distearyl dimethyl ammonium chloride, two hydrogenated-tallow group alkyl dimethyl ammonium chlorides, three (dodecyl) ammonio methacrylate, three (tetradecyl) ammonio methacrylate, three (hexadecyl) ammonio methacrylate, three (octadecyl) ammonio methacrylate, or corresponding bromide, it is used alone or as a mixture.
4. according to the method for claim 1, it is characterized in that described coupling agent is selected from:
I) titanate coupling agent shown in the following general formula:
(R
1O)
m-(Ti-OX
1-R′-Y
1)
n，
1≤m≤4 wherein, m+n≤6, R
1Be the saturated alkyl of 1-4 carbon atom, R ' is the saturated alkyl of 1-24 carbon atom or the aryl of 7-20 carbon atom; X
1Be groups such as C=O, O-P=O; Y
1Be groups such as hydroxyl, amino, epoxy group(ing), alkenyl, preferred two fat acyloxy metatitanic acid second diester, isopropoxy tricarboxylic acyl titanate, two (dioctylphosphatos)) metatitanic acid second diester;
Silane coupling agent shown in the ii) following general formula:
Y
2-(CH
2CH
2-)
o-Si-X
2 3，
Wherein o is 2～30, Y
2Be organo-functional group, as vinyl, methacryloyl, epoxy group(ing), amino, sulfydryl etc., X
2Be hydrolysable group, as halogen, alkoxyl group, acyloxy etc., preferred long-chain saturated alkane silane coupling agent (8-30 carbon atom), γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan, γ-(methacryloxypropyl) oxypropyl trimethyl oxosilane;
Aluminium titanium composite coupler shown in the iii) following general formula:
R wherein
3Saturated or unsaturated alkyl for 1-24 carbon atom.
5. according to the method for claim 1, it is characterized in that described dispersion medium is water, sherwood oil, toluene, acetone, ethanol.
6. according to the method for claim 1, it is characterized in that the interlamellar spacing from the modified montmorillonoid of step a) is 2.0-5.5nm, be 2.0-5.5nm from the interlamellar spacing of the modified montmorillonoid of step b).
7. polyhutadiene/Nano composite material of montmorillonite, comprise polyhutadiene and be scattered in wherein by the modified montmorillonoid that obtains as each method among the claim 1-6, wherein the number-average molecular weight scope of polyhutadiene is 1-60 * 10
4, preferred 1-3 * 10
5, and polynite content is 0.5-50 weight part/100 weight part polyhutadiene, more preferably 0.5-15 weight part/100 weight part polyhutadiene.
8. a method for preparing as the desired polyhutadiene/Nano composite material of montmorillonite of claim 7 comprises the steps:
A) cationite is to the intercalation modifying of polynite: under agitation with the 0.5-10 weight part, the ratio of preferred 1-5 weight part/100ml is scattered in the dispersion medium, forms stable montmorillonite suspension liquid with natural montmorillonite; Individually with cationite with the 0.5-15 weight part, the ratio of preferred 1-10 weight part/100ml is dissolved in the dispersion medium, forms solution; At 50-100 ℃, under preferred 60-85 ℃ the temperature this solution is added in the montmorillonite suspension liquid, stirred 1-8 hour, preferred 3-6 hour, suction filtration and washing 60 ℃ of following vacuum-dryings, made the polynite of cationite intercalation modifying then;
B) coupling agent is to the surperficial coupling modification of the product of step a): will be from the polynite of the cationite intercalation modifying of the first step with the 0.5-10 weight part 60-90 ℃ temperature and under stirring, the ratio of preferred 1-5 weight part/100ml is scattered in the 100 weight part dispersion medium, and to add based on the polynite from the cationite intercalation modifying of the first step in whipping process be 0.1-10 weight %, the coupling agent of preferred 0.5-5 weight %, continue then to stir 10-90 minute, preferred 10-30 minute, remove dispersion medium, vacuum-drying makes the polynite of cationite intercalation modifying and surperficial coupling modification;
C) modified montmorillonoid that step b) is obtained joins in the dispersion medium, it is even to be stirred to system, be made into the organic modification montmorillonite dispersions, wherein the proportioning of the dispersion liquid of organic modification polynite is 1-10 weight part organic modification polynite/100ml dispersion medium;
D) hydrocarbon organic solvent, divinyl, optional polar additive and the organic modification montmorillonite dispersions of step c) are added in the reactor, evenly stir, form stable divinyl/organic modification montmorillonite dispersions, be warming up to 30-80 ℃, add organic lithium initiator, begin to carry out polyreaction, wherein the consumption of organic lithium initiator is selected according to the size of required polyhutadiene number-average molecular weight;
E) after the divinyl total overall reaction finishes, add terminator, stop polyreaction, and randomly add conventional additives, adopt traditional method that the polymkeric substance glue is carried out aftertreatment then, obtain polyhutadiene/Nano composite material of montmorillonite behind the product drying.
9. method according to Claim 8, wherein hydrocarbon organic solvent is selected from benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, Mixed XYLENE, raffinates oil or its mixture, is preferably selected from one or both the mixture in hexanaphthene and the toluene.
10. method according to Claim 8, wherein polar additive is selected from nitrogenous compound, as triethylamine, Tetramethyl Ethylene Diamine, two piperidines ethane; Or P contained compound such as HMPA.
11. method according to Claim 8, wherein organic lithium initiator is selected from the mixture of simple function group organolithium, bifunctional organolithium, polyfunctional group organolithium or several organic lithium initiators.Organic lithium initiator can be represented by the formula: R (Li) x, and R is the alkyl that contains 1-20 carbon atom, and R can be alkyl or aryl, and x is the integer of 1-8.
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| CN102241403A (en) * | 2011-05-10 | 2011-11-16 | 中国地质大学（北京） | Anionic-cationic composite intercalation type organic montmorillonite material and preparation method thereof |
| CN102295295A (en) * | 2011-06-13 | 2011-12-28 | 中国石油化工股份有限公司 | Method for preparing organoclay by using composite organic modifier |
| CN102372274A (en) * | 2010-08-16 | 2012-03-14 | 中国水产科学研究院东海水产研究所 | Preparation method for bifunctional-modified montmorillonite dispersion liquid |
| CN101792152B (en) * | 2009-09-23 | 2012-04-11 | 江苏强林生物能源有限公司 | Abietyl quaternary ammonium salt-modified organic nano imvite, preparation method thereof and use thereof |
| CN102874825A (en) * | 2012-10-17 | 2013-01-16 | 南通南京大学材料工程技术研究院 | Compound modification method for clay |
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| CN107282000A (en) * | 2017-07-20 | 2017-10-24 | 安徽国能亿盛环保科技有限公司 | A kind of preparation method of modified silver type bentonite organic wastewater adsorbent |
| CN108239424A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院化学研究所 | A kind of transparent silane-modified nano imvite dispersion liquid and its preparation method and application |
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| CN111423619A (en) * | 2020-04-30 | 2020-07-17 | 北京东方雨虹防水技术股份有限公司 | Hydrophobic flame-retardant modified montmorillonite, preparation method thereof, hydrophobic dustproof flame-retardant thermoplastic polyolefin waterproof material and application |
| CN111995885A (en) * | 2020-07-14 | 2020-11-27 | 南京工业大学 | Method for modifying organic montmorillonite by composite modifier |
| CN112646273A (en) * | 2020-12-22 | 2021-04-13 | 江苏尚艾新材料科技有限公司 | Polypropylene composite material with high light transmittance, hydrolysis resistance, antibiosis and mildew resistance and preparation method thereof |
| CN112897543A (en) * | 2019-12-04 | 2021-06-04 | 中国石油天然气股份有限公司 | Method for reducing particle size of kaolin fine powder |
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| CN114853026A (en) * | 2022-03-30 | 2022-08-05 | 哈工大机器人集团(杭州湾)国际创新研究院 | Preparation method of high-performance lithium bentonite |
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-
2004
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| CN101792152B (en) * | 2009-09-23 | 2012-04-11 | 江苏强林生物能源有限公司 | Abietyl quaternary ammonium salt-modified organic nano imvite, preparation method thereof and use thereof |
| CN102372274A (en) * | 2010-08-16 | 2012-03-14 | 中国水产科学研究院东海水产研究所 | Preparation method for bifunctional-modified montmorillonite dispersion liquid |
| CN102372274B (en) * | 2010-08-16 | 2013-03-13 | 中国水产科学研究院东海水产研究所 | Preparation method for bifunctional-modified montmorillonite dispersion liquid |
| CN102241403B (en) * | 2011-05-10 | 2013-03-13 | 中国地质大学（北京） | Anionic-cationic composite intercalation type organic montmorillonite material and preparation method thereof |
| CN102241403A (en) * | 2011-05-10 | 2011-11-16 | 中国地质大学（北京） | Anionic-cationic composite intercalation type organic montmorillonite material and preparation method thereof |
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| CN102874825A (en) * | 2012-10-17 | 2013-01-16 | 南通南京大学材料工程技术研究院 | Compound modification method for clay |
| CN102874825B (en) * | 2012-10-17 | 2014-10-08 | 南通南京大学材料工程技术研究院 | Compound modification method for clay |
| CN103432993B (en) * | 2013-09-09 | 2015-05-20 | 内蒙古润隆化工有限责任公司 | Modified bentonite composite purifier and preparation method thereof |
| CN103432993A (en) * | 2013-09-09 | 2013-12-11 | 内蒙古润隆化工有限责任公司 | Modified bentonite composite purifier and preparation method thereof |
| CN103881423A (en) * | 2014-03-24 | 2014-06-25 | 浙江丰虹新材料股份有限公司 | Easily-dispersible organic clay with reactivity and preparation method thereof |
| CN103881423B (en) * | 2014-03-24 | 2016-06-29 | 浙江丰虹新材料股份有限公司 | A kind of easily dispersion has reactive organic clay and preparation method thereof |
| CN108239424A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院化学研究所 | A kind of transparent silane-modified nano imvite dispersion liquid and its preparation method and application |
| CN106750438A (en) * | 2017-02-16 | 2017-05-31 | 中山大学 | A kind of water/oxygen barrier polymer based composites and its preparation method and application |
| CN107282000A (en) * | 2017-07-20 | 2017-10-24 | 安徽国能亿盛环保科技有限公司 | A kind of preparation method of modified silver type bentonite organic wastewater adsorbent |
| CN110527500A (en) * | 2018-05-24 | 2019-12-03 | 中国石油化工股份有限公司 | White oil base drilling fluid method for preparing organobentonite |
| CN110773165A (en) * | 2019-11-05 | 2020-02-11 | 中催技术有限公司 | Preparation method of catalyst for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
| CN110773165B (en) * | 2019-11-05 | 2022-07-08 | 中催技术有限公司 | Preparation method of catalyst for synthesizing ethylene glycol by dimethyl oxalate hydrogenation |
| CN112897543A (en) * | 2019-12-04 | 2021-06-04 | 中国石油天然气股份有限公司 | Method for reducing particle size of kaolin fine powder |
| CN111423619A (en) * | 2020-04-30 | 2020-07-17 | 北京东方雨虹防水技术股份有限公司 | Hydrophobic flame-retardant modified montmorillonite, preparation method thereof, hydrophobic dustproof flame-retardant thermoplastic polyolefin waterproof material and application |
| CN111995885A (en) * | 2020-07-14 | 2020-11-27 | 南京工业大学 | Method for modifying organic montmorillonite by composite modifier |
| CN112646273A (en) * | 2020-12-22 | 2021-04-13 | 江苏尚艾新材料科技有限公司 | Polypropylene composite material with high light transmittance, hydrolysis resistance, antibiosis and mildew resistance and preparation method thereof |
| CN113214439A (en) * | 2021-06-02 | 2021-08-06 | 宁波锋成先进能源材料研究院有限公司 | Nano active agent material, preparation method and application thereof |
| CN113214439B (en) * | 2021-06-02 | 2023-02-21 | 宁波锋成先进能源材料研究院有限公司 | Nano active agent material and preparation method and application thereof |
| CN114249969A (en) * | 2021-12-07 | 2022-03-29 | 宁波东旭成新材料科技有限公司 | Preparation method of thermal-stability optical reflecting film |
| CN114680133B (en) * | 2022-03-18 | 2023-11-03 | 湖南工业大学 | Metal organic framework/montmorillonite composite material and preparation method and application thereof |
| CN114680133A (en) * | 2022-03-18 | 2022-07-01 | 湖南工业大学 | Metal organic framework/montmorillonite composite material and preparation method and application thereof |
| CN114853026A (en) * | 2022-03-30 | 2022-08-05 | 哈工大机器人集团(杭州湾)国际创新研究院 | Preparation method of high-performance lithium bentonite |
| CN114853026B (en) * | 2022-03-30 | 2023-08-08 | 哈工大机器人集团(杭州湾)国际创新研究院 | Preparation method of high-performance lithium bentonite |
| CN116200937B (en) * | 2023-04-28 | 2023-09-01 | 江苏米格新材料股份有限公司 | Composite heat insulation felt and preparation method thereof |
| CN116200937A (en) * | 2023-04-28 | 2023-06-02 | 江苏米格新材料有限公司 | Composite heat insulation felt and preparation method thereof |
| CN117801181A (en) * | 2024-02-27 | 2024-04-02 | 烟台舜康生物科技有限公司 | Method for preparing organic-inorganic nanocomposite material by UV photopolymerization |
| CN117801181B (en) * | 2024-02-27 | 2024-05-14 | 烟台舜康生物科技有限公司 | Method for preparing organic-inorganic nanocomposite material by UV photopolymerization |
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