CN100545185C - Butadiene isoprene copolymer/clay nanocomposites and preparation method thereof - Google Patents
Butadiene isoprene copolymer/clay nanocomposites and preparation method thereof Download PDFInfo
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- CN100545185C CN100545185C CNB2005100679263A CN200510067926A CN100545185C CN 100545185 C CN100545185 C CN 100545185C CN B2005100679263 A CNB2005100679263 A CN B2005100679263A CN 200510067926 A CN200510067926 A CN 200510067926A CN 100545185 C CN100545185 C CN 100545185C
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Abstract
The present invention relates to class butadiene isoprene copolymer/clay nanocomposites and preparation method thereof, by adopting classical anionic solution polymerization method, with the lithium alkylide is initiator, the hydro carbons organic reagent is a solvent, polar additive is a structure regulator, by processing that clay is effectively organised, realized the in-situ inserted polymerization of divinyl and isoprene monomer, a prepared class butadiene isoprene copolymer/clay nanocomposites has excellent more mechanical property, resistance toheat, barrier property, resistance to chemical corrosion, over-all properties can reach balance preferably.
Description
Technical field
The present invention relates to class butadiene isoprene copolymer/clay nanocomposites and preparation method thereof.
Background technology
Polymer nanocomposites becomes more meticulous because of the height of its disperse phase and nanometer size effect has and conventional composite materials (micron order disperse phase) visibly different mechanical property and functionalization ability.Wherein, layered silicate/polymer nanocomposites has more outstanding or special performance with the high shape factor ratio of disperse phase (layered silicate crystal lamella) again, as: high rigidity, high strength, high-barrier, high flame retardant, resistance to chemical attack etc.The preparation method of layered silicate/polymer nanocomposites has three kinds usually: in-situ monomer intercalation polymerization, performed polymer intercalation method, polyalcohol intercalation method.Performed polymer intercalation method must make enough performed polymers be inserted into the organophilic clay interlayer as monomer, because performed polymer viscosity is apparently higher than monomer, thereby weakened the swelling capacity of performed polymer on the one hand to organophilic clay, also reduced reactivity and speed of response simultaneously.Therefore, reduce the viscosity of performed polymer, improve the consistency between performed polymer and organophilic clay or reactively become the difficult point of technology implementation for this reason.The polyalcohol intercalation method is that polymkeric substance is when fusion or solution state, physics or chemical action with polymkeric substance and organic modified silicate are the intercalation motivating force, directly insert between organically-modified silicate layer, thereby form layered silicate/polymer nanocomposites.For improving the consistency between polymkeric substance and organophilic clay, often to add suitable compatilizer, the compatilizer that requires to introduce should have stronger interaction with intercalator, perhaps the nonpolar part of compatilizer is answered sufficiently long, can provide steric hindrance on the one hand, the enlargement layer spacing weakens the interlayer magnetism, has improved the consistency with matrix polymer on the other hand.But during the large usage quantity of compatilizer, can produce adverse influence to the performance of material.The in-situ monomer intercalation polymerization is that organophilic clay is directly joined swelling in the monomer, monomer is at interlayer and in-situ polymerization takes place on every side, interlamellar spacing strengthens gradually with the carrying out of reaction, and final organophilic clay is dispersed in the polymkeric substance with individual layer, forms the organophilic clay polymer nanocomposites.The interaction of organic clay and polymkeric substance is stronger, and the consistency between organic clay and the polymkeric substance is better, thereby organic clay is uniformly dispersed, and material easily forms exfoliated structure, and organic clay is obvious to the reinforcing effect of polymeric matrix.As seen, the in-situ monomer intercalation polymerization is ideal effective complex method, and the interaction of organic clay and polymkeric substance is the strongest, and the consistency between organic clay and the polymkeric substance is best, and organic clay is the most remarkable to the reinforcing effect of polymeric matrix.
U.S. Pat 4889885 discloses two kinds of research methods that prepare clay/rubber-based nano composite material, the in-situ inserted polymerization of the first, promptly at first clay layer is carried out modification with the quaternary ammonium salt of end-vinyl, then this organic clay is dispersed in N, in the dinethylformamide solvent, the free radical type initiator that adds isoprene monomer and corresponding proportion, isoprene just between clay layer initiated polymerization become polyisoprene rubber, remove solvent, obtain clay/polyisoprene rubber nano composite material.It two is that the liquid amino terminated butadiene acrylonitrile rubber that molecular weight is lower is dispersed in the mixed solvent of being made up of water and methyl-sulphoxide, adding acid then makes it form ammonium salt, mix with the aqeous suspension of clay again, slough water and solvent at last, just formed clay/liquid acrylonitrile butadiene rubber nano composite material.
Patent WO97/00910 earlier with clay dispersion in water, because the hydration of interlayer cation, this layering is very fast and uniform, then sneak into monomer, initiator, emulsifying agent etc., in the water dispersion of clay crystal layer, carry out the letex polymerization of rubber, thus the preparation clay-rubber nm-class composite material.Be subjected to the restriction of emulsion particle diameter and micella size, this technology dispersed less better, the interface belongs to physical action, and reaction system is still too complicated, wayward, is difficult for industrialization.
Chinese patent ZL98101496.8 adopts macromole emulsion intercalation method, earlier clay is dispersed in the water with lower ratio, adds rubber latex then, clay layer is interted and isolates with the macromole latex particle, the latex particle diameter is more little, and dispersion effect is good more.At last, add altogether agent with fixed attention and make whole system coprecipitated, slough moisture content, obtain rubber/clay composite material.Matrix materials such as clay/SBR, clay/NBR, clay/XNBR, clay/NR, clay/CR have successfully been prepared with this technology.For improving the interface interaction effect, can in system, add multi-functional coupling molecule.This compounding 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 lower.Shortcoming is when clay content is higher, and dispersed not as reaction intercalation method, wastewater flow rate is also bigger.
Summary of the invention
Technical characterictic of the present invention is to be different from above-mentioned radical polymerization, emulsion polymerisation process, but by adopting classical anionic solution polymerization method, with the organolithium is that initiator, hydro carbons organic reagent are that solvent, polar additive are structure regulator, by processing that clay is effectively organised, realize the in-situ inserted polymerization of divinyl, isoprene monomer, prepare a class butadiene isoprene copolymer/clay nanocomposites, strengthen elastomerics with the preparation nanometer, improved the over-all properties of polymeric articles effectively.Simultaneously, compare with methods such as above-mentioned radical polymerization, letex polymerizations, of the present invention is that initiator anionic solution polymerization method is easy to microtexture, sequential structure, molecular parameter to butadiene isoprene copolymer etc. and regulates with the lithium alkylide, to prepare the butadiene isoprene copolymer/clay nanocomposites of seriation, this advantage of the present invention just place.
The object of the present invention is to provide a kind of butadiene isoprene copolymer/clay nanocomposites, prepared butadiene isoprene copolymer/the clay nanocomposites of the present invention has excellent more mechanical property, resistance toheat, barrier property, resistance to chemical corrosion, and over-all properties can reach balance preferably.
Another object of the present invention is to provide a kind of preparation method of butadiene isoprene copolymer/clay nanocomposites, preparation method of the present invention is a divinyl, the in-situ inserted polymerization of isoprene monomer: in conjunction with existing lithium is the butadiene isoprene copolymer production technique, pass through divinyl, the in-situ inserted polymerization of isoprene monomer, prepare a class butadiene isoprene copolymer/clay nanocomposites, the present invention utilizes polymer nanocomposites disperse phase height to become more meticulous and nanometer size effect improves the mechanical property and functionalization ability (as: the high rigidity of conventional composite materials, high strength, high-barrier, high flame retardant, chemicals-resistant corrosion etc.), make product have more outstanding characteristic.The prepared butadiene isoprene copolymer of methods such as features such as employing is the prepared butadiene isoprene copolymer of method of initiator anionic solution polymerization with the lithium alkylide, its microtexture and above-mentioned radical polymerization, letex polymerization is far different.
The invention provides a kind of butadiene isoprene copolymer/clay nanocomposites, comprise butadiene isoprene copolymer and the clay that is scattered in wherein, wherein, the number-average molecular weight general range of butadiene isoprene copolymer is 1 * 10
4-60 * 10
4, preferred range is 5 * 10
4-40 * 10
4, optimum range is 10 * 10
4-30 * 10
4The isoprene content general range is 10-90 weight % in the butadiene isoprene copolymer, and preferred range is 30-70 weight %, and the butadiene content general range is 10-90 weight %, and preferred range is 30-70 weight %; 1,2-structural content and 3,4-structural content sum general range is 5-100 weight %, 1,4-structural content general range is 95-0 weight %.The clay content general range is 0.5-50 part heavy clay/100 parts heavy butadiene isoprene copolymers.
Clay content general range of the present invention is 0.5-50 part heavy clay/100 parts heavy butadiene isoprene copolymers, preferred range is 1-30 part heavy clay/100 parts heavy butadiene isoprene copolymers, and optimum range is 1-15 part heavy clay/100 parts heavy butadiene isoprene copolymers.When clay content was low, clay was not enough to produce enough enhancements, and when clay content was higher, material was Powdered, is difficult to machine-shaping.
The present invention also provides the preparation method of a class butadiene isoprene copolymer/clay nanocomposites, comprise hydrocarbon organic solvent, divinylic monomer, isoprene monomer, optional polar additive and the intercalation clay that is scattered in the dispersion medium add in the reactor, stir, form stable divinyl, isoprene/intercalation clay dispersion liquid, be warming up to 30-80 ℃, add organic lithium initiator, carry out polyreaction, after divinyl and the end of isoprene total overall reaction, termination reaction obtains clay/butadiene isoprene copolymer nano composite material.
Details are as follows for the preparation method of butadiene isoprene copolymer/clay nanocomposites of the present invention:
1 with montmorillonitic clay through intercalator handle organic clay.
2 join organic clay in a certain amount of dispersion medium, and it is even to be stirred to system, is made into the organic clay dispersion liquid, and the proportioning of organic clay dispersion liquid is 1-10g organic clay/100ml dispersion medium.
3 join divinyl, isoprene monomer in the reactor by monomer ratio in hydrocarbon organic solvent, monomer concentration is 10-20 weight %, press the clay consumption and add certain proportion organic clay dispersion liquid, optionally can select for use polar additive to regulate the microtexture of butadiene isoprene copolymer, open stirring, guarantee that system is even, form stable divinyl, isoprene/organic clay dispersion liquid, after reaching kick off temperature, the initiation reaction temperature is 30-80 ℃, add organic lithium initiator, polyreaction begins to carry out.The consumption of organic lithium initiator is decided according to the size of butadiene isoprene copolymer number-average molecular weight, and the number-average molecular weight scope of butadiene isoprene copolymer is generally 1 * 10
4-60 * 10
4The consumption of polar additive is looked its kind, butadiene isoprene copolymer 1 because of the difference of polarity power, 2-structural content and 3, and the height of 4-structural content sum and deciding, 1,2-structural content and 3,4-structural content sum general range is 5-100 weight %.
4 after divinyl, isoprene monomer total overall reaction finish, add terminator, stop polyreaction, also can randomly add conventional additives, as anti-aging agent Irganox 1010 (trade(brand)name, Ciba-Geigy company is on sale) and Antigene BHT or 2.6.4 (trade(brand)name, SUMITOMO CHEMICAL KCC is on sale), adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain butadiene isoprene copolymer/clay nanocomposites.
Hydrocarbon organic solvent of the present invention, divinylic monomer, isoprene monomer, optional polar additive and the intercalation clay addition sequence that is scattered in the dispersion medium are not key factor, and it can successively add, and also can add simultaneously.The consumption of intercalation clay is so that contain the heavy butadiene isoprene copolymers of 0.5-50 part heavy clay/100 parts and be advisable in the butadiene isoprene copolymer/clay nanocomposites of gained.
Intercalation clay of the present invention (organic clay) can be commercially available intercalation clay, and as the intercalation clay that Zhejiang Feng Hong clay chemical industry company limited provides, it is nano imvite (a fine powder body).Intercalation clay also can be obtained after the intercalator intercalation processing by clay.Described clay can be selected from montmorillonite, hectorite, saponite, sauconite, vermiculite, beidellite, hectorite, green stone, silica, halloysite, talcum powder, magadiite, fibrous morphology crystals, illite mineral, stratiform aluminum phosphate or zirconium, and the mixture of above-mentioned substance; Be the lamellar aluminosilicate that content is no less than 85% montmorillonite preferably with mineralogical composition, more preferably mineralogical composition is the lamellar aluminosilicate that content is no less than 95% montmorillonite, its unit cell is made up of two-layer silicon-oxy tetrahedron therebetween layer of aluminum oxygen octahedra, connect by shared Sauerstoffatom between the two, montmorillonitic clay layer internal surface has negative charge, interlayer cation Na
+, Ca
2+, Mg
2+Deng being the interchangeability positively charged ion, through delaminating dispersion, the remodeling of purifying, super-fine classified, organic being composited.Positively charged ion in the clay gets intercalation clay (organic clay) after intercalator (ion-exchanger) exchange is handled, it can make the polymer monomer intercalation to interlayer, as the method for available US4889885 clay is handled.Be used for the lamellar aluminosilicate that the preferred smectite content of montmorillonitic clay of the present invention is no less than 85 weight %, its particle size range is (1-70) * 10
3Nm, cation exchange capacity is between 40-200meg/100g.More preferably smectite content is no less than the lamellar aluminosilicate of 95 weight %, and its particle size range is (20-30) * 10
3Nm, cation exchange capacity are between the 90-110meg/100g.Described intercalator is selected from the organic ammonium class, can be secondary ammonium, three grades of ammoniums or level Four ammonium halide, as: palmityl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, dodecyl benzyl dimethyl ammonium chloride, distearyl dimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, cetyl trimethylammonium bromide, octadecyl trimethylammonium bromide, dodecyl dimethyl benzyl ammonium bromide, two octadecyl dimethyl brometo de amonio, Trimethyllaurylammonium bromide, it can be used alone or as a mixture.
Hydrocarbon organic solvent used in the present invention is selected from a kind of varsol in aromatic hydrocarbons and the aliphatic hydrocarbon or the mixture of several varsols, generally be selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, BTX aromatics (as: xylol), mixing-in fat hydrocarbon (as: raffinating oil) etc., preferably from: toluene, dimethylbenzene, hexane, hexanaphthene, raffinate oil.
Dispersion medium used in the present invention is selected from the mixture of one or more organic reagents in benzene, toluene, ethylbenzene, dimethylbenzene, BTX aromatics, ether, triethylamine, the HMPA.The preferred mixture of one or both in toluene, dimethylbenzene.
Polar additive used in the present invention 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(wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical also can be different, with R
1, R
2Be not all good, as glycol dimethyl ether, ethylene glycol diethyl ether), R
1OCH
2CH
2OCH
2CH
2OR
2(wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Can be identical also can be different, with R
1, R
2Be not all good, as diethylene glycol dimethyl ether, dibutyl ethylene glycol ether), crown ether; (2) nitrogenous compound generally is selected from: triethylamine, Tetramethyl Ethylene Diamine (TMEDA), two piperidines ethane (DPE), preferred TMEDA; (3) P contained compound is generally selected HMPA (HMPA) for use.
Initiator used in the present invention is an organic lithium initiator, is selected from the mixture of a kind of simple function group organic lithium initiator, bifunctional organic lithium initiator, multifunctional group organic lithium initiator 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 the mixture of a kind of simple function group organic lithium initiator or several simple function group organic lithium initiators, generally be selected from: lithium methide, lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, uncle's octyl group lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-phenyl butyl lithium, cyclohexyl lithium etc.
Initiator used in the present invention can be the disclosed any bifunctional organic lithium initiator of prior art, be selected from the mixture of a kind of bifunctional organic lithium initiator or several bifunctional organic lithium initiators, generally be selected from: two lithiums of (1) two haloalkane hydro carbons and the two lithiums of oligopolymer thereof, its structural formula is LiR
*Li, Li (DO) nR
*(DO) nLi, wherein: R
*For 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 1,3-pentadiene, isoprene are 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, butadiene isoprene copolymer 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, the two lithiums, 1 of 1 '-(1, the 3-penylene)-two [3-methyl isophthalic acid-(4-tolyl) 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 can be the disclosed any multifunctional group organic lithium initiator of prior art, is 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 Pb, 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
nAlso can be to contain above-mentioned metal species multifunctional group organic lithium initiator T (R
#Li) n, polyfunctional group lithium 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 CN1148053A
#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.
The used terminator of the present invention is the disclosed any terminator that can be used for anionic polymerisation of prior art, as water, methyl alcohol, ethanol or Virahol etc.
Description of drawings
Accompanying drawing 1 is the X-ray diffractogram of butadiene isoprene copolymer/clay nanocomposites of obtaining among the embodiment 1.
Accompanying drawing 2 is the transmission electron microscope photo of butadiene isoprene copolymer/clay nanocomposites of obtaining among the embodiment 1.
Accompanying drawing 3 is thermal weight loss (TGA) graphic representation of butadiene isoprene copolymer/clay nanocomposites of obtaining among the embodiment 1.
Embodiment
Further specify the present invention below in conjunction with embodiment, Comparative Examples, but and the scope of unrestricted claim protection of the present invention.
Used analytical instrument and the test condition of following embodiment products therefrom is as follows:
1 second-order transition temperature T
gDetect and adopt du pont company TA2910 type differential scanning calorimeter, 20 ℃/min of heat-up rate.
2 thermal weight loss core temperature T
DcDetect to adopt the du pont company TA2980 type difference analyser of reheating, 100-600 ℃ of detected temperatures scope, nitrogen atmosphere.
The 3X-ray diffraction peaks detects and adopts Japanese D/maxRB type x-ray analysis instrument of science, 12KWX ray, note spectrum scanning continuously, CuK α radiation, back monochromator, tube voltage 40kV, tube current 100mA, sweep limit 1-25 °, 2 °/min of sweep velocity.
4 butadiene isoprene copolymer microtextures detect the employing U.S. AVANCE-400 of BRUKER company type NMR analyser, and (solvent is CDCl
3).
5 transmission electron microscopes (TEM): the TECNAI G of FEI Co.
220 electronic transmission Electronic Speculum, 200KV acceleration voltage, freezing microtome section.
The organic clay that is adopted among the following embodiment (intercalation clay) is a nano imvite (fine powder body), is provided by Zhejiang Feng Hong clay chemical industry company limited, and product grade is NANNOLIN DK4, and smectite content is 95%-98 weight %, and median size is 25 * 10
3Nm, density is 1.8g/cm
3, apparent density is 0.45g/cm
3, average wafer thickness is less than 25nm, and moisture content is less than 3 weight %, and the cationic exchange total volume is 110meg/100g.The interlamellar spacing of original soil is 1.2nm, and the interlamellar spacing of organic clay is 3.59nm.The organic clay dispersion liquid is that organic clay is added in the dispersion medium, obtains after stirring.
Embodiment 1
In the 500ml reactor, add 72g hexanaphthene and 9g monomer, the mass ratio that set of monomers becomes divinyl and isoprene is 5: 5, add polar additive Tetramethyl Ethylene Diamine (TMEDA) again, TMEDA/Li (mol ratio) is 0.2, the intercalation clay dispersion liquid (4g intercalation clay/100ml toluene) that adds 6.7ml at last, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.46ml (the n-Butyl Lithium volumetric molar concentration is 0.1315mol/l), react and add 0.2ml terminator ethanol after 6 hours, add 0.2g anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4) again, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain butadiene isoprene copolymer/clay nanocomposites.Product butadiene isoprene copolymer/clay nanocomposites 1, the 2-PB structural content is 8.9 weight %, 1, the 4-PB structural content is 42.6 weight %, 1, the 4-PIp structural content is 42.7 weight %, 3, and the 4-PIp structural content is 5.8 weight %, intercalation clay content is 3.0 weight %, second-order transition temperature T
gBe-73.0 ℃, thermal weight loss core temperature T
DcBe 451.4 ℃ of (Fig. 3, thermal weight loss core temperature T of butadiene isoprene copolymer pure sample
DcIt is 436.4 ℃).The X-ray detection does not have the obvious diffraction peak in 1 °～10 °, show that montmorillonite layer peels off fully in polymeric matrix, has formed exfoliated nano-composite (Fig. 1).TEM detects and to show that also the intercalation clay lamella peels off each other, separates fully, is state of disarray, is dispersed in the matrix, is exfoliated (delaminated) matrix material (Fig. 2).
In the 500ml reactor, add 72g hexanaphthene and 9g monomer, the mass ratio that set of monomers becomes divinyl and isoprene is 3: 7, add polar additive Tetramethyl Ethylene Diamine (TMEDA) again, TMEDA/Li (mol ratio) is 0.2, the intercalation clay dispersion liquid (4g intercalation clay/100ml toluene) that adds 2.3ml at last, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.46ml (the n-Butyl Lithium volumetric molar concentration is 0.1315mol/l), react and add 0.2ml terminator ethanol after 6 hours, add 0.2g anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4) again, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain butadiene isoprene copolymer/clay nanocomposites.Product butadiene isoprene copolymer/clay nanocomposites 1, the 2-PB structural content is 5.8 weight %, 1, the 4-PB structural content is 25.0 weight %, 1, the 4-PIp structural content is 60.1 weight %, 3, and the 4-PIp structural content is 9.1 weight %, intercalation clay content is 1.0 weight %, second-order transition temperature T
gBe-63.1 ℃, thermal weight loss core temperature T
DcBe 450.4 ℃ of (thermal weight loss core temperature T of butadiene isoprene copolymer pure sample
DcIt is 432.4 ℃).The X-ray detection does not have the obvious diffraction peak in 1 °～10 °, show that montmorillonite layer peels off fully in polymeric matrix, has formed exfoliated nano-composite.TEM detects and to show that also the intercalation clay lamella peels off each other, separates fully, is state of disarray, is dispersed in the matrix, is exfoliated (delaminated) matrix material.
Embodiment 3
In the 500ml reactor, add 72g hexanaphthene and 9g monomer, the mass ratio that set of monomers becomes divinyl and isoprene is 5: 5, add polar additive Tetramethyl Ethylene Diamine (TMEDA) again, TMEDA/Li (mol ratio) is 0.2, the intercalation clay dispersion liquid (4g intercalation clay/100ml toluene) that adds 4.6ml at last, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.46ml (the n-Butyl Lithium volumetric molar concentration is 0.1315mol/l), react and add 0.2ml terminator ethanol 0.2ml after 6 hours, add 0.2g anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4) 0.2g again, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain butadiene isoprene copolymer/clay nanocomposites.Product butadiene isoprene copolymer/clay nanocomposites 1, the 2-PB structural content is 8.1 weight %, 1, the 4-PB structural content is 42.2 weight %, 1, the 4-PIp structural content is 44.1 weight %, 3, and the 4-PIp structural content is 5.6 weight %, intercalation clay content is 2.0 weight %, second-order transition temperature T
gBe-72.5 ℃, thermal weight loss core temperature T
DcIt is 451.0 ℃.The X-ray detection does not have the obvious diffraction peak in 1 °～10 °, show that montmorillonite layer peels off fully in polymeric matrix, has formed exfoliated nano-composite.TEM detects and to show that also the intercalation clay lamella peels off each other, separates fully, is state of disarray, is dispersed in the matrix, is exfoliated (delaminated) matrix material.
In the 500ml reactor, add 72g hexanaphthene and 9g monomer, the mass ratio that set of monomers becomes divinyl and isoprene is 5: 5, add polar additive Tetramethyl Ethylene Diamine (TMEDA) again, TMEDA/Li (mol ratio) is 0.2, the intercalation clay dispersion liquid (4g intercalation clay/100ml toluene) that adds 11.8ml at last, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.46ml (the n-Butyl Lithium volumetric molar concentration is 0.1315mol/l), react and add 0.2ml terminator ethanol after 6 hours, add 0.2g anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4) again, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain butadiene isoprene copolymer/clay nanocomposites.Product butadiene isoprene copolymer/clay nanocomposites 1, the 2-PB structural content is 8.2 weight %, 1, the 4-PB structural content is 42.9 weight %, 1, the 4-PIp structural content is 43.0 weight %, 3, and the 4-PIp structural content is 5.9 weight %, intercalation clay content is 5.0 weight %, second-order transition temperature T
gBe-73.3 ℃, thermal weight loss core temperature T
DcIt is 452.4 ℃.The X-ray detection does not have the obvious diffraction peak in 1 °～10 °, show that montmorillonite layer peels off fully in polymeric matrix, has formed exfoliated nano-composite.TEM detects and to show that also the intercalation clay lamella peels off each other, separates fully, is state of disarray, is dispersed in the matrix, is exfoliated (delaminated) matrix material.
Embodiment 5
In the 500ml reactor, add 72g hexanaphthene and 9g monomer, the mass ratio that set of monomers becomes divinyl and isoprene is 5: 5, add polar additive Tetramethyl Ethylene Diamine (TMEDA) again, TMEDA/Li (mol ratio) is 0.5, the intercalation clay dispersion liquid (4g intercalation clay/100ml toluene) that adds 6.7ml at last, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.46ml (the n-Butyl Lithium volumetric molar concentration is 0.1315mol/l), react and add 0.2ml terminator ethanol after 6 hours, add 0.2g anti-aging agent (1010 with weight ratio 1: 1 mix with 2.6.4) again, adopt traditional method that the polymkeric substance glue is carried out aftertreatment, carry out analytical test behind the product drying, obtain butadiene isoprene copolymer/clay nanocomposites.Product butadiene isoprene copolymer/clay nanocomposites 1, the 2-PB structural content is 28.0 weight %, 1, the 4-PB structural content is 22.0 weight %, 1, the 4-PIp structural content is 20.5 weight %, 3, and the 4-PIp structural content is 29.5 weight %, intercalation clay content is 3.0 weight %, second-order transition temperature T
gBe-52.5 ℃, thermal weight loss core temperature T
DcIt is 451.2 ℃.The X-ray detection does not have the obvious diffraction peak in 1 °～10 °, show that montmorillonite layer peels off fully in polymeric matrix, has formed exfoliated nano-composite.TEM detects and to show that also the intercalation clay lamella peels off each other, separates fully, is state of disarray, is dispersed in the matrix, is exfoliated (delaminated) matrix material.
Claims (18)
1. the preparation method of a class butadiene isoprene copolymer/clay nanocomposites, comprise hydrocarbon organic solvent, divinylic monomer, isoprene monomer, optional polar additive and the intercalation clay that is scattered in the dispersion medium add in the reactor, stir, form stable divinyl, isoprene/intercalation clay dispersion liquid, be warming up to 30 ℃-80 ℃, add organic lithium initiator, carry out polyreaction, work as divinyl, after the isoprene monomer total overall reaction finishes, termination reaction obtains clay/butadiene isoprene copolymer nano composite material.
2. according to the process of claim 1 wherein that described clay is the lamellar aluminosilicate that smectite content is no less than 85 weight %, its particle size range is (1-70) * 10
3Nm, cation exchange capacity is between 40-200meq/100g.
3. according to the method for claim 2, wherein said clay is the lamellar aluminosilicate that smectite content is no less than 95 weight %, and its particle size range is (20-30) * 10
3Nm, cation exchange capacity are between the 90-110meq/100g.
4. according to each method of claim 1-3, wherein hydrocarbon organic solvent be selected from by in benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, the group of forming of raffinating oil any one or multiple.
5. according to the method for claim 4, wherein hydrocarbon organic solvent be selected from by in toluene, dimethylbenzene, hexane, hexanaphthene, the group of forming of raffinating oil any one or multiple.
6. according to each method of claim 1-3, wherein polar additive is selected from oxygenatedchemicals, and this oxygenatedchemicals is ether, tetrahydrofuran (THF), crown ether compound, R
1OCH
2CH
2OR
2, R
1OCH
2CH
2OCH
2CH
2OR
2In one or more, R wherein
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Identical or different.
7. according to each method of claim 1-3, wherein polar additive is selected from nitrogenous compound, and this nitrogenous compound is one or more in triethylamine, Tetramethyl Ethylene Diamine, the two piperidines ethane.
8. according to each method of claim 1-3, wherein polar additive is selected from P contained compound, and this P contained compound is a HMPA.
9. according to each method of claim 1-3, wherein organic lithium initiator is selected from one or more in the simple function group organic lithium initiator, represents with following formula: RLi, R are alkyl or the aryl that contains 1-20 carbon atom.
10. according to the method for claim 9, wherein the simple function group organic lithium initiator is selected from one or more in the group of being made up of lithium methide, lithium ethide, sec.-propyl lithium, n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, uncle's octyl group lithium, phenyl lithium, 2-naphthyl lithium, 4-butyl phenyl lithium, 4-phenyl butyl lithium, cyclohexyl lithium.
11. according to each method of claim 1-3, wherein dispersion medium is selected from the mixture of one or more organic reagents in benzene, toluene, ethylbenzene, dimethylbenzene, ether, triethylamine, the HMPA.
12. according to the method for claim 11, wherein dispersion medium is selected from one or both the mixture in toluene, the dimethylbenzene.
13. butadiene isoprene copolymer/clay nanocomposites that the method for a class by claim 1 obtains, comprise butadiene isoprene copolymer and the clay that is scattered in wherein, wherein the number-average molecular weight scope of butadiene isoprene copolymer is 1 * 10
4-60 * 10
4The content of butadiene monomer unit is 10-90 weight %, the content of isoprene monomer unit is 10-90 weight %, 1,2-structural content and 3,4-structural content sum are 5-100 weight %, 1,4-structural content scope is 95-0 weight %, and the clay content scope is 0.5-50 part heavy clay/100 parts heavy butadiene isoprene copolymers.
14. butadiene isoprene copolymer/clay nanocomposites according to claim 13, wherein the number-average molecular weight scope of butadiene isoprene copolymer is 5 * 10
4-40 * 10
4
15. butadiene isoprene copolymer/clay nanocomposites according to claim 14, wherein the number-average molecular weight scope of butadiene isoprene copolymer is 10 * 10
4-30 * 10
4
16. butadiene isoprene copolymer/clay nanocomposites according to claim 13, wherein the content of butadiene monomer unit is 30-70 weight %, and the content of isoprene monomer unit is 30-70 weight %.
17. according to each described butadiene isoprene copolymer/clay nanocomposites of claim 13-16, wherein the clay content scope is 1-30 part heavy clay/100 parts heavy butadiene isoprene copolymers.
18. butadiene isoprene copolymer/clay nanocomposites according to claim 17, wherein the clay content scope is 1-15 part heavy clay/100 parts heavy butadiene isoprene copolymers.
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