CN1330701C - Butadiene-isoprene-styrene copolymer / clay nano composite materials and process for preparing same - Google Patents
Butadiene-isoprene-styrene copolymer / clay nano composite materials and process for preparing same Download PDFInfo
- Publication number
- CN1330701C CN1330701C CNB2004100376232A CN200410037623A CN1330701C CN 1330701 C CN1330701 C CN 1330701C CN B2004100376232 A CNB2004100376232 A CN B2004100376232A CN 200410037623 A CN200410037623 A CN 200410037623A CN 1330701 C CN1330701 C CN 1330701C
- Authority
- CN
- China
- Prior art keywords
- isoprene
- clay
- butadiene
- lithium
- styrol copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004927 clay Substances 0.000 title claims abstract description 158
- 229920001577 copolymer Polymers 0.000 title claims abstract description 79
- 239000002114 nanocomposite Substances 0.000 title claims description 58
- 239000000463 material Substances 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 80
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 54
- 230000002687 intercalation Effects 0.000 claims abstract description 46
- 238000009830 intercalation Methods 0.000 claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 18
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- -1 Alkyl lithium Chemical compound 0.000 claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000003999 initiator Substances 0.000 claims description 43
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 41
- 239000000178 monomer Substances 0.000 claims description 38
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 22
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002612 dispersion medium Substances 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910021647 smectite Inorganic materials 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 claims description 3
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims description 2
- RFVYQWYNYFCXQL-UHFFFAOYSA-N C1=CC=CC2=CC([Li])=CC=C21 Chemical compound C1=CC=CC2=CC([Li])=CC=C21 RFVYQWYNYFCXQL-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- SEVZJBPKDJZGFW-UHFFFAOYSA-N [Li]C1=CC=C(CCCC)C=C1 Chemical compound [Li]C1=CC=C(CCCC)C=C1 SEVZJBPKDJZGFW-UHFFFAOYSA-N 0.000 claims description 2
- ZEDXYOJKIFJKHK-UHFFFAOYSA-N [Li]CCCCC1=CC=CC=C1 Chemical compound [Li]CCCCC1=CC=CC=C1 ZEDXYOJKIFJKHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003053 piperidines Chemical class 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 24
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
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- 239000002904 solvent Substances 0.000 abstract description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
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- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 1
- 150000001450 anions Chemical class 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
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- 241000446313 Lamella Species 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 6
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- 238000010438 heat treatment Methods 0.000 description 6
- 239000000138 intercalating agent Substances 0.000 description 6
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 230000000977 initiatory effect Effects 0.000 description 3
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
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- 229910000271 hectorite Inorganic materials 0.000 description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 2
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
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- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
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- 125000002091 cationic group Chemical group 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229910000276 sauconite Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a butadiene-isoprene-styrene copolymer / clay nanometer composite material and a preparation method. Alkyl lithium is used as an activating agent, a hydrocarbon organic reagent is used as a solvent, and a polarity additive agent is used as a microstructure adjusting agent by adopting a classical anion solution polymerization method, and the intercalation polymerization of the original position of butadiene, isoprene and styrene monomer can be achieved by that the clay is effectively and organically treated. The prepared butadiene-isoprene-styrene copolymer / clay nanometer composite material has the advantages of excellent mechanical performance, heat resistant performance, diaphragming performance and chemical corrosion resistant performance; the comprehensive performance can reach better balance.
Description
Technical field
The present invention relates to class butadiene-isoprene-styrol 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 intercalator of require introducing should with interlayer modified dose stronger interaction is arranged, perhaps the nonpolar part of intercalator 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 N-dimethyl formyl ammonium solvent, the free radical type initiator that adds isoprene monomer and corresponding proportion, isoprene just between clay layer initiated polymerization become butadiene-isoprene-styrol copolymer rubber, remove solvent, obtain clay/butadiene-isoprene-styrol copolymer rubber nano composite material.It two is that the liquid end ammonium paracril that molecular weight is lower is dispersed in the mixed solvent of being made up of water and dimethoxy sulphur, 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 CN1238353A (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 initiator, the hydro carbons organic reagent is a solvent, polar additive is a structure regulator, by processing that clay is effectively organised, realize divinyl, isoprene, the in-situ inserted polymerization of styrene monomer, prepare a class butadiene-isoprene-styrol 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, molecular parameter to butadiene-isoprene-styrol copolymer etc. and regulates with the lithium alkylide, with butadiene-isoprene-styrol copolymer/clay nanocomposites of preparing seriation, this advantage of the present invention just place.
The object of the present invention is to provide a kind of butadiene-isoprene-styrol copolymer/clay nanocomposites, prepared butadiene-isoprene-styrol 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 the preparation method of a kind of butadiene-isoprene-styrol copolymer/clay nanocomposites, preparation method of the present invention is a divinyl, isoprene, the in-situ inserted polymerization of styrene monomer: in conjunction with existing lithium based polymer production technique, pass through divinyl, isoprene, the in-situ inserted polymerization of styrene monomer, prepare a class butadiene-isoprene-styrol 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.Prepared butadiene-isoprene-the styrol copolymer of methods such as features such as employing is the prepared butadiene-isoprene-styrol 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-styrol copolymer/clay nanocomposites, comprise butadiene-isoprene-styrol copolymer and the clay that is scattered in wherein, wherein, the number-average molecular weight general range of butadiene-isoprene-styrol 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 content of styrene monomer is 10-50% (weight percent), preferred 15-35% (weight percent); The content sum of divinyl, isoprene monomer is 50-90% (weight percent), preferred 65-85% (weight percent), and the weight ratio of divinyl and isoprene monomer is 10/90 to 90/10, more preferably 30/70 to 70/30; 1,2-structural content and 3,4-structural content sum general range is 5%-100% (weight percent), 1,4-structural content general range is 95%-0% (weight percent).The clay content general range is 0.5-50 part heavy clay/100 parts heavy butadiene-isoprene-styrol copolymers.
Clay content general range of the present invention is 0.5-50 part heavy clay/100 parts heavy butadiene-isoprene-styrol copolymers, preferred range is 1-30 part heavy clay/100 parts heavy butadiene-isoprene-styrol copolymers, and optimum range is 1-15 part heavy clay/100 parts heavy butadiene-isoprene-styrol 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-styrol copolymer/clay nanocomposites, comprise hydrocarbon organic solvent, divinylic monomer, isoprene monomer, styrene monomer, optional polar additive and the intercalation clay that is scattered in the dispersion medium add in the reactor, stir, form stable divinyl, isoprene, vinylbenzene/intercalation clay dispersion liquid, be warming up to 30 ℃-80 ℃, add organic lithium initiator, carry out polyreaction, work as divinyl, isoprene, after the vinylbenzene total overall reaction finishes, termination reaction obtains clay/butadiene-isoprene-styrol copolymer nano composite material.
Details are as follows for the preparation method of butadiene-isoprene-styrol copolymer of the present invention/clay nanocomposites:
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 press monomer ratio in hydrocarbon organic solvent, order of addition(of ingredients) is with divinylic monomer, isoprene monomer, styrene monomer joins in the reactor, monomer concentration is 10%-20% (weight percent), 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-styrol copolymer, open stirring, guarantee that system is even, form stable divinyl, isoprene, vinylbenzene/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-styrol copolymer number-average molecular weight, and the number-average molecular weight scope of butadiene-isoprene-styrol copolymer is generally 1 * 10
4-60 * 10
4The consumption of polar additive is looked its kind, butadiene-isoprene-styrol copolymer 1 because of the difference of polarity power, 2-structural content and 3, the height of 4-structural content and decide 1,2-structural content and 3,4-structural content sum general range is 5%-100% (weight percent).
4 after divinyl, isoprene, styrene monomer total overall reaction finish, add terminator, stop polyreaction, also can randomly add conventional additives, as anti-aging agent Irganox1010 (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-styrol copolymer/clay nanocomposites.
Hydrocarbon organic solvent of the present invention, divinylic monomer, isoprene monomer, styrene 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-styrol copolymers of 0.5-50 part heavy clay/100 parts and be advisable in the butadiene-isoprene-styrol copolymer of gained/clay nanocomposites.
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 percent), 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 percent), 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, three second ammoniums, hexamethyl phosphinylidyne three ammoniums.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, tetrahydrochysene bark mutter, 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: three second ammoniums, tetramethyl-second two ammoniums (TMEDA), two piperidines ethane (DPE), preferred TMEDA; (3) P contained compound is generally selected hexamethyl phosphinylidyne three ammoniums (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, the 3-isoprene, 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, butadiene-isoprene-styrol copolymer two lithium oligopolymers, butadiene-isoprene-styrol 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, 1,1 '-(1, the 3-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, 1,1 '-(1, the 3-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, 1,1 '-(1, the 4-penylene)-two [3-methyl isophthalic acid-(4-tolyl) amyl group] two lithiums, 1,1 '-(1, the 4-penylene)-two two lithiums of [3-methyl isophthalic acid-(4-tolyl) amyl group] isoprene oligopolymer, the two lithiums of 1,1 '-(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
#Lin, 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
#Lin contains above-mentioned metal species multifunctional group organic lithium initiator T (R
#Li) n, polyfunctional group lithium initiator T (R
#Li) n generally is selected from stanniferous class multifunctional group organic lithium initiator Sn (R
#Li) n is as the stanniferous class multifunctional group organic lithium initiator Sn (R that mentions among the patent CN1148053A
#Li) 4.The polyfunctional group lithium initiator can also be that other functionality that can be used in initiation isoprene, 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 transmission electron microscope photo of butadiene-isoprene-styrol copolymer/clay nanocomposites of embodiment 2.
Accompanying drawing 2 is the transmission electron microscope photo of butadiene-isoprene-styrol copolymer/clay nanocomposites of embodiment 1.
Accompanying drawing 3 is the x-ray diffraction pattern of butadiene-isoprene-styrol copolymer/clay nanocomposites.
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 the speed that heats up.
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-isoprenes-styrol copolymer microtexture detects and adopts the U.S. NMR of BRUKE company analyser.
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), Feng Hong clay chemical industry company limited provides by Zhejiang, product grade is NANNOLINDK4, and smectite content is 95%-98% (weight percent), 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 percent), 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, during monomer is formed, divinyl, isoprene, cinnamic mass content is respectively 35%, 35%, 30%, add polar additive tetramethyl-second two ammoniums (TMEDA) again, TMEDA/Li (mol ratio) is 1.0, the intercalation clay dispersion liquid (4g intercalation clay/100ml toluene) that adds 7.0ml at last, begin to stir, heating and constant temperature are at 50 ℃, (the n-Butyl Lithium volumetric molar concentration is 0.1315mol/l to add the required n-Butyl Lithium 0.46ml of initiation, solvent is a hexanaphthene, down together), react and add terminator ethanol after 6 hours, add 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-styrol copolymer/clay nanocomposites.Product butadiene-isoprene-styrol copolymer/clay nanocomposites styrene content is 22.2% (weight percent), in the polyhutadiene 1, the 2-structural content is in 27.8% (weight percent), the polyhutadiene 1, the 4-structural content is 27.1% (weight percent), in the polyisoprene 3, the 4-structural content is in 15.2% (weight percent), the polyisoprene 1, the 4-structural content is 7.7% (weight percent), intercalation clay content is 3.0% (weight percent), second-order transition temperature T
gBe-29.7 ℃, thermal weight loss core temperature T
Dc[the peak temperature of choosing the thermal weight loss differential curve is thermal weight loss core temperature T to be 440.0 ℃
Dc, referring to Ma Jisheng, QiZongNeng, Zhang Shufan, synthetic, the structure of composite polyurethane elastomer/montmorillonoid nano-material and performance, the polymer journal, 3 (3), 325 (2001), down with].The x-ray diffraction pattern of intercalation clay is not seen the curve a of Fig. 3; And the x-ray diffraction pattern of butadiene-isoprene-styrol copolymer/clay nanocomposites is seen the curve c of Fig. 3.Can find out that from accompanying drawing 3 001 diffraction peak of curve (a) is in 2.46 °, pairing interlamellar spacing is 3.59nm; And butadiene-isoprene-styrol copolymer/clay nanocomposites (curve (c)) does not have the obvious diffraction peak in 1 °～10 °, shows that montmorillonite layer peels off fully in polymeric matrix, has formed exfoliated nano-composite (accompanying drawing 3).TEM detects and to show that also the intercalation clay lamella peels off each other, separates fully, is state of disarray, is dispersed in divinyl, isoprene and the styrol copolymer, is exfoliated (delaminated) matrix material (seeing accompanying drawing 2).
Embodiment 2
In the 500ml reactor, add 72g hexanaphthene and 9g monomer, during monomer is formed, divinyl, isoprene, cinnamic mass content is respectively 35%, 35%, 30%, add polar additive tetramethyl-second two ammoniums (TMEDA) again, TMEDA/Li (mol ratio) is 1.0, 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 terminator ethanol after 6 hours, add 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-styrol copolymer/clay nanocomposites.Product butadiene-isoprene-styrol copolymer/clay nanocomposites styrene content is 24.6% (weight percent), in the polyhutadiene 1, the 2-structural content is in 32.9% (weight percent), the polyhutadiene 1, the 4-structural content is 23.1% (weight percent), in the polyisoprene 3, the 4-structural content is in 18.7% (weight percent), the polyisoprene 1, the 4-structural content is 0.7% (weight percent), intercalation clay content is 1.0% (weight percent), second-order transition temperature T
gBe-15.1 ℃, thermal weight loss core temperature T
DcIt is 428.8 ℃.The x-ray diffraction pattern of butadiene-isoprene-styrol copolymer/clay nanocomposites is seen the curve b of Fig. 3.Can find out that from accompanying drawing 3 001 diffraction peak of curve (a) is in 2.46 °, pairing interlamellar spacing is 3.59nm; And butadiene-isoprene-styrol copolymer/clay nanocomposites (curve (b)) does not have the obvious diffraction peak in 1 °～10 °, shows 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 divinyl, isoprene and the styrol copolymer, is exfoliated (delaminated) matrix material (seeing accompanying drawing 1).
Embodiment 3
In the 500ml reactor, add 72g hexanaphthene and 9g monomer, during monomer is formed, divinyl, isoprene, cinnamic mass content is respectively 35%, 35%, 30%, add polar additive tetramethyl-second two ammoniums (TMEDA) again, TMEDA/Li (mol ratio) is 1.0, the intercalation clay dispersion liquid (4g intercalation clay/100ml toluene) that adds 7.0ml at last, begin to stir, heating and constant temperature are at 50 ℃, add and cause required n-Butyl Lithium 0.34ml (the n-Butyl Lithium volumetric molar concentration is 0.1315mol/l), react and add terminator ethanol after 6 hours, add 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-styrol copolymer/clay nanocomposites.Product butadiene-isoprene-styrol copolymer/clay nanocomposites styrene content is 22.6% (weight percent), in the polyhutadiene 1, the 2-structural content is in 28.8% (weight percent), the polyhutadiene 1, the 4-structural content is 26.4% (weight percent), in the polyisoprene 3, the 4-structural content is in 15.6% (weight percent), the polyisoprene 1, the 4-structural content is 6.6% (weight percent), intercalation clay content is 3.0% (weight percent), second-order transition temperature T
gBe-28.1 ℃, thermal weight loss core temperature T
DcIt is 440.8 ℃.X-ray and TEM detect demonstration intercalation clay lamella and peel off each other, separate fully, are state of disarray, are dispersed in divinyl, isoprene and the styrol copolymer, are exfoliated (delaminated) matrix material.
Embodiment 4
In the 500ml reactor, add 72g toluene and 9g monomer, during monomer is formed, divinyl, isoprene, cinnamic mass content is respectively 35%, 35%, 30%, add polar additive tetramethyl-second two ammoniums (TMEDA) again, TMEDA/Li (mol ratio) is 1.0, the intercalation clay dispersion liquid (4g intercalation clay/100ml toluene) that adds 11.7ml 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 terminator ethanol after 6 hours, add 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-styrol copolymer/clay nanocomposites.Product butadiene-isoprene-styrol copolymer/clay nanocomposites styrene content is 17.3% (weight percent), in the polyhutadiene 1, the 2-structural content is in 26.0% (weight percent), the polyhutadiene 1, the 4-structural content is 35.0% (weight percent), in the polyisoprene 3, the 4-structural content is in 12.5% (weight percent), the polyisoprene 1, the 4-structural content is 9.2% (weight percent), intercalation clay content is 5.0% (weight percent), second-order transition temperature T
gBe-39.6 ℃, thermal weight loss core temperature T
DcIt is 432.6 ℃.The x-ray diffraction pattern of butadiene-isoprene-styrol copolymer/clay nanocomposites is seen the curve d of Fig. 3.Can find out that from accompanying drawing 3 001 diffraction peak of curve (a) is in 2.46 °, pairing interlamellar spacing is 3.59nm; And butadiene-isoprene-styrol copolymer/clay nanocomposites (curve (d)) does not have the obvious diffraction peak in 1 °～10 °, shows 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 divinyl, isoprene and the styrol copolymer, is exfoliated (delaminated) matrix material.
Embodiment 5
In the 500ml reactor, add 72g dimethylbenzene and 9g monomer, during monomer is formed, divinyl, isoprene, cinnamic mass content is respectively 50%, 30%, 20%, add polar additive tetramethyl-second two ammoniums (TMEDA) again, TMEDA/Li (mol ratio) is 0.5, the intercalation clay dispersion liquid (4g intercalation clay/100ml toluene) that adds 7.0ml 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 terminator ethanol after 6 hours, add 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-styrol copolymer/clay nanocomposites.Product butadiene-isoprene-styrol copolymer/clay nanocomposites styrene content is 18.6% (weight percent), in the polyhutadiene 1, the 2-structural content is in 30.0% (weight percent), the polyhutadiene 1, the 4-structural content is 23.5% (weight percent), in the polyisoprene 3, the 4-structural content is in 17.6% (weight percent), the polyisoprene 1, the 4-structural content is 10.3% (weight percent), intercalation clay content is 3.0% (weight percent), second-order transition temperature T
gBe-23.2 ℃, thermal weight loss core temperature T
DcIt is 435.6 ℃.X-ray and TEM detect demonstration intercalation clay lamella and peel off each other, separate fully, are state of disarray, are dispersed in divinyl, isoprene and the styrol copolymer, are exfoliated (delaminated) matrix material.
Comparative Examples
In the 500ml reactor, add 72g toluene and 9g monomer, during monomer is formed, divinyl, isoprene, cinnamic mass content is respectively 35%, 35%, 30%, add polar additive tetramethyl-second two ammoniums (TMEDA) again, TMEDA/Li (mol ratio) is 1.0, 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 terminator ethanol after 6 hours, add 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-styrol copolymer/clay nanocomposites.Product butadiene-isoprene-styrol copolymer/clay nanocomposites styrene content is 23.8% (weight percent), in the polyhutadiene 1, the 2-structural content is in 33.2% (weight percent), the polyhutadiene 1, the 4-structural content is 21.4% (weight percent), in the polyisoprene 3, the 4-structural content is in 21.1% (weight percent), the polyisoprene 1, and the 4-structural content is 0.5% (weight percent), second-order transition temperature T
gBe-10.0 ℃, thermal weight loss core temperature T
DcIt is 425.1 ℃.
Claims (18)
1. a class butadiene-isoprene-styrol copolymer/clay nanocomposites comprises butadiene-isoprene-styrol copolymer and the clay that is scattered in wherein, and wherein, the number-average molecular weight scope of butadiene-isoprene-styrol copolymer is 1 * 10
4-60 * 10
4The content of styrene monomer is 10-50% by weight percentage, the content sum of divinyl, isoprene monomer is 50-90% by weight percentage, the weight ratio of divinyl and isoprene monomer is 10/90 to 90/10,1,2-structural content and 3,4-structural content sum is 5%-100% by weight percentage, 1,4-structural content scope is 95%-0% by weight percentage, and the clay content scope is 0.5-50 part heavy clay/100 parts heavy butadiene-isoprene-styrol copolymers.
2. butadiene-isoprene-styrol copolymer according to claim 1/clay nanocomposites, wherein the number-average molecular weight scope of butadiene-isoprene-styrol copolymer is 5 * 10
4-40 * 10
4
3. butadiene-isoprene-styrol copolymer according to claim 2/clay nanocomposites, wherein the number-average molecular weight scope of butadiene-isoprene-styrol copolymer is 10 * 10
4-30 * 10
4
4. butadiene-isoprene-styrol copolymer according to claim 1/clay nanocomposites, wherein the content of styrene monomer is 15-35% by weight percentage, the content sum of divinyl, isoprene monomer is 65-85% by weight percentage, and the weight ratio of divinyl and isoprene monomer is 30/70 to 70/30.
5. according to each described butadiene-isoprene-styrol copolymer/clay nanocomposites of claim 1-4, wherein the clay content scope is 1-30 part heavy clay/100 parts heavy butadiene-isoprene-styrol copolymers.
6. butadiene-isoprene-styrol copolymer according to claim 5/clay nanocomposites, wherein the clay content scope is 1-15 part heavy clay/100 parts heavy butadiene-isoprene-styrol copolymers.
7. the preparation method of a class butadiene-isoprene-styrol copolymer/clay nanocomposites, comprise hydrocarbon organic solvent, divinylic monomer, isoprene monomer, styrene monomer, optional polar additive and the intercalation clay that is scattered in the dispersion medium add in the reactor, stir, form stable divinyl, isoprene, vinylbenzene/intercalation clay dispersion liquid, be warming up to 30 ℃-80 ℃, add organic lithium initiator, carry out polyreaction, work as divinyl, isoprene, after the styrene monomer total overall reaction finishes, termination reaction obtains clay/butadiene-isoprene-styrol copolymer nano composite material.
8. the preparation method of butadiene-isoprene-styrol copolymer according to claim 7/clay nanocomposites, it is characterized in that described clay is that smectite content is no less than 85% lamellar aluminosilicate by weight percentage, its particle size range is 1 * 10
3-70 * 10
3Nm, cation exchange capacity is between 40-200meg/100g.
9. the preparation method of butadiene-isoprene-styrol copolymer according to claim 8/clay nanocomposites, it is characterized in that described clay is that smectite content is no less than 95% lamellar aluminosilicate by weight percentage, its particle size range is 20 * 10
3-30 * 10
3Nm, cation exchange capacity are between the 90-110meg/100g.
10. according to each method of claim 7-9, wherein hydrocarbon organic solvent is selected from: benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexanaphthene, xylol, raffinate oil.
11. according to the method for claim 10, wherein hydrocarbon organic solvent is selected from: toluene, dimethylbenzene, hexane, hexanaphthene, raffinate oil.
12. according to each method of claim 7-9, wherein polar additive is selected from oxygenatedchemicals: ether, tetrahydrofuran (THF), crown ether compound, R
1OCH
2CH
2OR
2, R
1OCH
2CH
2OCH
2CH
2OR
2, wherein: R
1, R
2Be that carbonatoms is the alkyl of 1-6, R
1, R
2Identical or different.
13. according to each method of claim 7-9, wherein polar additive is selected from nitrogenous compound: triethylamine, Tetramethyl Ethylene Diamine, two piperidines ethane.
14. according to each method of claim 7-9, wherein polar additive is selected from P contained compound: HMPA.
15. according to each method of claim 7-9, 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 the alkyl that contains 1-20 carbon atom, R is alkyl or aryl.
16. according to the method for claim 15, wherein the simple function group organic lithium initiator is 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.
17. according to each method of claim 7-9, wherein dispersion medium is selected from the mixture of one or more organic reagents in benzene, toluene, ethylbenzene, dimethylbenzene, BTX aromatics, ether, triethylamine, the HMPA.
18. according to the method for claim 17, wherein dispersion medium is selected from one or both the mixture in toluene, the dimethylbenzene.
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| CNB2004100376232A CN1330701C (en) | 2004-04-28 | 2004-04-28 | Butadiene-isoprene-styrene copolymer / clay nano composite materials and process for preparing same |
| PCT/CN2005/000588 WO2005105856A1 (en) | 2004-04-28 | 2005-04-28 | A polymer/clay nanocomposite and process for the production thereof |
| EP05752485.2A EP1757625B1 (en) | 2004-04-28 | 2005-04-28 | A polymer/clay nanocomposite and process for the production thereof |
| JP2007509856A JP5405739B2 (en) | 2004-04-28 | 2005-04-28 | Polymer / clay nanocomposite materials and methods for their preparation |
| US11/119,425 US20050282948A1 (en) | 2004-04-28 | 2005-04-28 | Polymer/clay nanocomposite materials and process for the preparation thereof |
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| CNB2004100376232A CN1330701C (en) | 2004-04-28 | 2004-04-28 | Butadiene-isoprene-styrene copolymer / clay nano composite materials and process for preparing same |
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| US5883173A (en) * | 1995-06-23 | 1999-03-16 | Exxon Research And Engineering Company | Nanocomposite materials (LAW392) |
| CN1446834A (en) * | 2003-04-02 | 2003-10-08 | 华东理工大学 | Block copolymer and preparation method as well as tis application in preparing composite materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5883173A (en) * | 1995-06-23 | 1999-03-16 | Exxon Research And Engineering Company | Nanocomposite materials (LAW392) |
| CN1446834A (en) * | 2003-04-02 | 2003-10-08 | 华东理工大学 | Block copolymer and preparation method as well as tis application in preparing composite materials |
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| Title |
|---|
| 聚合物纳米材料研究进展 夏和生，王琪，化学研究与应用，第14卷第2期 2002 * |
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